Supporting Information hydroboration of carbonyl compounds · S1 Supporting Information Reusable...

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Supporting Information

Reusable Fe2O3-nanoparticles catalysed efficient and selective

hydroboration of carbonyl compounds

Mahadev L. Shegavi,a Ashim Baishya,b K. Geetharani*b and Shubhankar Kumar Bose*a

a Centre for Nano and Material Sciences (CNMS), JAIN (Deemed-to-be University), Jain Global Campus, Bangalore-562112 (India).b Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore-560012 (India).

Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.This journal is © the Partner Organisations 2018

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Index

I. General Information………………………….……………………………..………..…S3

II. Experiment Details…………………….....……………………..….....……..…..…S4-S13

III. Spectroscopic Data of Hydroboration Products and Relevant Alcohols.….….......S14-S24

IV. NMR Spectra of Hydroboration Products and Relevant Alcohols ………….....…S25-S79

V. Competitive Chemoselective Hydroboration Reactions………….....................…S80-S86

VI. Mechanistic Investigations……………………………………………..……...….S87-S92

VII. References ………………………...…………………….….………….………........…S93

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I. General Information

All reagents were purchased from Avra, Alfa-Aesar or Aldrich and were used as

received. The iron precursor Fe(NO3)3·9H2O and Fe2O3 (nanopowder, <50 nm particle size)

were purchased from Aldrich. C6D6 and CDCl3 were purchased from Cambridge Isotope

Laboratories and were dried using molecular sieves and deoxygenated using the freeze-

pump-thaw method. HBpin for bulk reactions was prepared from B2pin2 according to

literature procedures.1a Fe2O3 nanoparticles were prepared according to the literature

procedure.1b Commercially available, pre-coated TLC-sheets ALUGRAM® Xtra Sil G/UV254

was purchased from MACHEREY-NAGEL GmbH & Co. KG. The removal of solvent was

performed on a rotary evaporator in vacuo at a maximum temperature of 40 °C.

All NMR spectra were recorded at ambient temperature using a Bruker Avance 400

NMR spectrometer (1H, 400 MHz; 13C, 100 MHz; 11B, 128 MHz). 1H NMR chemical shifts

are reported relative to TMS and were referenced via residual proton resonances of the

corresponding deuterated solvent (CDCl3: 7.26 ppm, C6D6: 7.16 ppm) whereas 13C NMR

spectra are reported relative to TMS using the carbon signals of the deuterated solvent

(CDCl3: 77.16 ppm, C6D6: 128.06 ppm). 11B NMR signals were quoted relative to BF3·Et2O

and 19F NMR signals were quoted using FCCl3 as an internal standard. All 11B and 13C NMR

spectra were broad-band 1H decoupled. The IR spectra were obtained with a BRUKER

ALPHA spectrometer in the range of 400 to 4000 cm−1 using KBr windows. GC-MS data

were acquired using SHIMADZU GCMS QP 2010SE system.

The microstructure of the Fe2O3 NPs was studied by Rigaku Ultima IV powder X-ray

diffractometer using Cu Kα radiation (scan rate of 3° min−1). Scanning electron microscopy

(SEM) and Energy-dispersive X-ray spectroscopic (EDX) spectra were performed on a JSM

7100F JEOL FESEM with EDS, and TEM was carried out using JEOL transmission electron

microscope operating at 200 kV after casting a drop of nanoparticle dispersion in isopropyl

alcohol over Cu grid.

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II. Experimental Details

Synthesis of Fe2O3 nanoparticles.1 To a solution of Fe(NO3)3·9H2O (500 mL, 0.1M),

aqueous ammonia was added dropwise using dropping funnel with constant stirring until the

pH of the solution reached 10. The obtained precipitate was filtered off and washed several

times with distilled water. The product was dried in oven at 70 °C for 24 h followed by

calcined at 500 °C in a muffle furnace for 5 h. The Fe2O3 nanoparticles were characterised by

using field emission scanning electron microscope (FE-SEM), transmission electron

microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and powder XRD (X-ray

diffraction).

Figure S1. FESEM image of Fe2O3 nanoparticles.

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Figure S2. TEM images and particle size distribution chart of Fe2O3 nanoparticles.

The nanoparticle formed is characterized by transmission electron microscopy (TEM). The

TEM images demonstrated that the nanoparticles were having particle size in the range of 19-

62 nm and an average particle size of ∼33.4 nm.

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Figure S3. EDX spectrum and overlay map of Fe2O3 nanoparticles.

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20 40 60 80

0

2000

4000

6000

8000

Inte

nsity

(a.u

.)

2-theta (degree)

Figure S4. Powder XRD pattern of Fe2O3 nanoparticles.

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Table S1. Optimizations of the reaction conditions for the Fe2O3 nanoparticle catalysed hydroboration of benzaldehyde (1a).a

BO

OH+

Fe-catalystO

H

O

H

Bpin

Hsolvent (1 mL)RT

Entry Catalyst (mol%)

Temperature (°C)

Time (h)

HBpin (equiv)

Solvent (1 mL)

Product Yield (%)b

1 Fe2O3 NPs (5) RT 1 1.2 Toluene 54



4 Fe2O3 NPs (5) RT 8 1.2 Toluene >99

5 FeCl3·6H2O (5) RT 8 1.2 Toluene 22

6 Fe(NO3)3·9H2O (5) RT 8 1.2 Toluene 10

7 FeBr2 (5) RT 8 1.2 Toluene 19

8 FeCl3 (5) RT 8 1.2 Toluene trace

9c Fe2O3 (5) RT 8 1.2 Toluene 45

10d Fe2O3 (5) RT 8 1.2 Toluene 92

10 - RT 8 1.2 Toluene 5




14 Fe2O3 NPs (5) RT 8 1.2 Benzene 98

15 Fe2O3 NPs (5) RT 8 1.2 MTBE 88

16 Fe2O3 NPs (5) RT 8 1.2 Et2O 98

17e Fe2O3 NPs (5) RT 8 1.2 Toluene 90

a Reactions were carried out using 0.25 mmol of 1a (1 equiv), 1.2 equiv of HBpin (0.30 mmol) in 1 mL of solvent at room temperature unless otherwise stated. b Yields were determined by 1H NMR analysis, using nitromethane as an internal standard and are average of two experiments. c Reaction was performed using commercially available bulk Fe2O3. d Reaction was performed using commercially available Fe2O3 NPs (nanopowder, <50 nm particle size). e Reaction performed in air.

Experimental procedures for examples described in Table 1.

In a 10 mL thick-walled reaction tube equipped with a magnetic stirring bar, Fe-catalyst

(0.0125 mmol), HBpin (0.3 mmol), benzaldehyde (0.25 mmol) and solvent (1 mL) were

added. The reaction mixture was stirred at room temperature for the indicated amount of

time, then diluted with Et2O (2 mL) and filtered through a plug of celite (∅ 3 mm × 8 mm).

The solvents were removed in vacuo, and nitromethane was added as an internal standard.

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The product yield was determined by 1H NMR spectroscopy using nitromethane as an

internal standard.

General procedure of hydroborations of aldehydes (examples described in Tables 2). In

a 10 mL thick-walled reaction tube equipped with a magnetic stirring bar, Fe2O3 NPs (5 mol

%, 2 mg, 0.0125 mmol), HBpin (1.2 equiv, 44 µL, 0.3 mmol), toluene (1 mL) and aldehyde

(0.25 mmol) were added and the reaction was stirred vigorously at room temperature for 8 h.

The reaction mixture was then diluted with Et2O (2 mL) and filtered through a plug of celite

(∅ 3 mm × 8 mm) with copious washing (Et2O). The solvents were removed in vacuo, and

the borate ester yield was determined by 1H NMR spectroscopy using nitromethane as an

internal standard.

General procedure of hydroborations of ketones (examples described in Tables 3). In a

10 mL thick-walled reaction tube equipped with a magnetic stirring bar, Fe2O3 NPs (5 mol %,

2 mg, 0.0125 mmol), HBpin (1.2 equiv, 44 µL, 0.3 mmol), toluene (1 mL) and ketone (0.25

mmol) were added and the reaction mixture was stirred vigorously at room temperature for

18 h. The reaction mixture was then diluted with Et2O (2 mL) and filtered through a plug of

celite (∅ 3 mm × 8 mm) with copious washing (Et2O). The solvents were removed in vacuo,

and the borate ester yield was determined by 1H NMR spectroscopy using nitromethane as an

internal standard.

Experimental procedures for catalytic conversion of aldehydes/ketones to 1o/2o alcohols:

In a 50 mL round bottom flask equipped with a magnetic stirring bar, 5 mol % of Fe2O3 (5

mol %, 0.05 mmol, 8 mg), HBpin (1.2 mmol, 174 μL), toluene (4 mL) and aldehyde (1.0

mmol) were added. The resulting reaction mixture was stirred vigorously at room

temperature for 8 h (for ketone 18 h) and the progress of the reaction was monitored by TLC.

After completion of the reaction, it was diluted with diethyl ether (10 mL) and filtered

through a plug of celite (∅ 3 mm × 8 mm). The solvents were removed in vacuo, and then

methanol (5 mL) and 1N HCl (1 mL) were added to the reaction mixture and was refluxed at

50 ºC for 1 h (for ketone 3 h). The organic layer was extracted with dichloromethane (3 x 10

mL) and was removed by vacuum to get the crude compound. The crude residue was purified

by silica gel column chromatography using a mixture of hexane and ethyl acetate as eluent

and characterized by 1H and 13C NMR spectroscopy.

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Alternative hydrolysis method: The resulted borate ester residue was hydrolysed with silica

gel at 50 °C for 2-4 h. Then the organic layer was extracted with dichloromethane (3 x 10

mL) and the volatiles were removed under vacuum and the residue was purified by silica gel

column chromatography using a mixture of hexane and ethyl acetate as eluent.

General procedure for preparative scale reactions.

In a 100 mL round bottom flask equipped with a magnetic stirring bar, 10 mol % of Fe2O3

(0.5 mmol, 80 mg), HBpin (1.2 equiv, 6.0 mmol, 0.87 mL), toluene (10 mL) and aldehyde

(5.0 mmol) were added. The resulting reaction mixture was stirred vigorously at room

temperature for 8 h and the progress of the reaction was monitored by TLC. After completion

of the reaction, it was diluted with diethyl ether (50 mL) and filtered through a plug of celite.

The solvents were removed in vacuo, and then methanol (10 mL) and 1N HCl (2 mL) were

added to the reaction mixture and was refluxed at 50 ºC for 1 h. The organic layer was

extracted with dichloromethane (3 x 20 mL) and was removed by vacuum to get the crude

compound. The crude residue was purified by silica gel column chromatography using a

mixture of hexane and ethyl acetate as eluent and characterized by 1H and 13C NMR

spectroscopy.

The hydroboration of 4-bromobenzaldehyde (7a, 0.925 gm, 5 mmol), 2-

methylbenzaldehyde (11a, 0.6 gm, 5 mmol) and 1-naphthaldehyde (12a, 0.781 gm, 5 mmol)

gave the desired alcohols in good yields (7c: 0.804 gm, 87%; 11c: 0.439 gm, 73% and 12c:

0.484 gm, 62%).

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Table S2. Hydroboration of aldehydes catalysed by Fe2O3 NPs.a

a Reaction conditions: Aldehyde (1.0 mmol), Fe2O3 NPs (5 mol %, 0.05 mmol, 8 mg), HBpin (1.2 mmol, 174 μL) and toluene (2 mL), at room temperature for 18 h unless otherwise stated. b The yields were determined by 1H NMR analysis using nitromethane as an internal standard. c Isolated yield after chromatographic workup. d Reaction was performed using 2.2. equiv of HBpin.

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Table S3. Hydroboration of ketones catalysed by Fe2O3 NPs.a

a Reaction conditions: ketone (1.0 mmol), Fe2O3 NPs (5 mol %, 0.05 mmol, 8 mg), HBpin (1.2 mmol, 174 μL) and toluene (2 mL), at room temperature for 18 h unless otherwise stated. b The yields were determined by 1H NMR analysis using nitromethane as an internal standard. c Isolated yield after chromatographic workup.

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Table S4. Solvent effect on the Fe2O3 nanoparticle catalysed hydroboration of 4-bromobenzaldehyde (7a).a

BO

OH+

Fe2O3 NPs (5 mol %)O

H

O

H

Bpin

HRTBr Br


Temperature (°C)

Time (h)

HBpin (equiv)

Solvent (1 mL)

Product Yield (%)b

1 Fe2O3 NPs (5) RT 8 1.2 Toluene >99

2 Fe2O3 NPs (5) RT 8 1.2 - 84

3 - RT 8 1.2 - 18

a Reactions were carried out using 0.25 mmol of 7a (1 equiv), 1.2 equiv of HBpin (0.30 mmol) in 1 mL of solvent at room temperature unless otherwise stated. b Yields were determined by 1H NMR analysis, using nitromethane as an internal standard.

Table S5. Solvent effect on the Fe2O3 nanoparticle catalysed hydroboration of acetophenone (17a).a

BO

OH+

Fe2O3 NPs (5 mol %)O O

Bpin

HRT


Temperature (°C)

Time (h)

HBpin (equiv)

Solvent (1 mL)

Product Yield (%)b


2 Fe2O3 NPs (5) RT 18 1.2 - 73

a Reactions were carried out using 0.25 mmol of 17a (1 equiv), 1.2 equiv of HBpin (0.30 mmol) in 1 mL of solvent at room temperature unless otherwise stated. b Yields were determined by 1H NMR analysis, using nitromethane as an internal standard.

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III. Spectroscopic Data of Hydroboration Products and Relevant Alcohols

2-(Benzyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 1b).2,3 1H NMR (400

MHz, CDCl3, ppm): δ 7.38-7.29 (m, 5H), 4.96 (s, 2H), 1.30 (s, 12H). 11B

NMR (128 MHz, CDCl3, ppm): δ 22.4.

Phenylmethanol (1c).2,4 Colourless oil. Yield: 80% (86 mg). 1H NMR (400 MHz, CDCl3, ppm): δ 7.39-7.32 (m, 5H), 4.65 (s, 2H), 2.78 (br, 1H). 13C NMR (100 MHz,

CDCl3, ppm): δ 141.0, 128.7, 127.7, 127.1, 65.4.

4,4,5,5-Tetramethyl-2-((4-methylbenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 2b).2,3 1H

NMR (400 MHz, CDCl3, ppm): δ 7.30 (d, J = 8 Hz, 2H), 7.20 (d, J = 8

Hz, 2H), 4.94 (s, 2H), 2.39 (s, 3H), 1.32 (s, 12H). 11B NMR (128 MHz,

CDCl3, ppm): δ 22.3.

p-Tolylmethanol (2c).2,4 Colourless oil. Yield: 69% (84 mg). 1H NMR (400 MHz, CDCl3,

ppm): δ 7.21 (d, J = 8 Hz, 2H), 7.14 (d, J = 8 Hz, 2H), 4.58 (s, 2H), 2.33 (s,

3H), 2.09 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 138.0, 137.4, 129.3,

127.2, 65.2, 21.2.

2-((4-Methoxybenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 3b).2,3 1H

NMR (400 MHz, CDCl3, ppm): δ 7.33 (d, J = 8 Hz, 2H), 6.92 (d, J

= 8 Hz, 2H), 4.90 (s, 2H), 3.84 (s, 3H), 1.31 (s, 12H). 11B NMR

(128 MHz, CDCl3, ppm): δ 22.4.

OH

HH

H

OB O

O

H

OH

H

OB O

O

H

OB O

O

MeO

S15

(4-Methoxyphenyl)methanol (3c).2,5 Colourless oil. Yield: 70% (97 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.26 (d, J = 8 Hz, 2H), 6.89 (d, J = 8 Hz, 2H),

4.56 (s, 2H), 3.80 (s, 3H), 2.79 (br, 1H). 13C NMR (100 MHz, CDCl3,

ppm): δ 159.1, 133.2, 128.7, 113.9, 64.7, 55.3.

4-(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)phenol (Table 2, 4b).2,6 1H

NMR (400 MHz, CDCl3, ppm): δ 7.17 (d, J = 8 Hz, 2H), 6.80 (d, J =

8 Hz, 2H), 4.82 (s, 2H), 1.26 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.2.

2-((4-Fluorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 5b).2,8 1H

NMR (400 MHz, CDCl3, ppm): δ 7.35-7.31 (m, 2H), 7.04-7.00 (m, 2H),

4.89 (s, 2H), 1.27 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.4.

(4–Fluorophenyl)methanol (5c).2,5 Colourless oil. Yield: 86% (108 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.32-7.29 (m, 2H), 7.06-7.02 (m, 2H), 4.60 (s, 2H),

2.70 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 162.4 (d, JC–F = 244

Hz), 136.7 (d, JC–F = 3 Hz), 128.8 (d, JC–F = 8 Hz), 115.4 (d, JC–F = 20 Hz),

64.6. 19F NMR (376 MHz, CDCl3, ppm): -114.91.

2-((4-Chlorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 6b).2,3 1H

NMR (400 MHz, CDCl3, ppm): δ 7.37-7.33 (m, 2H), 7.07-7.02 (m,

2H), 4.91 (s, 2H), 1.29 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm):

δ 22.1.

H

OH

MeO

H

OB O

O

HO

H

OB O

O

F

H

OH

F

H

OB O

O

Cl

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(4–Chlorophenyl)methanol (6c).2,8 White solid. Yield: 63% (90 mg). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.32-7.30 (m, 2H), 7.24-7.22 (m, 2H), 4.57 (s, 2H), 3.07

(br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 139.3, 133.3, 128.7, 128.3,

64.3.

2-((4-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 7b).2,6 1H


Hz, 2H), 4.90 (s, 2H), 1.30 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.4.

(4–Bromophenyl)methanol (7c).2,5 White solid. Yield: 79% (148 mg). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.45 (d, J = 8 Hz, 2H), 7.15 (d, J = 8 Hz, 2H), 4.52 (s, 2H),

3.32 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 140.2, 132.0, 129.1,

121.8, 64.7.

4-(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)benzonitrile (Table 2,

8b).2,6 1H NMR (400 MHz, CDCl3, ppm): δ 7.63 (d, J = 8 Hz, 2H), 7.46

(d, J = 8 Hz, 2H), 4.99 (s, 2H), 1.27 (s, 12H). 11B NMR (128 MHz,


4-(Hydroxymethyl)benzonitrile (8c).2,8 White crystalline solid. Yield: 78% (102 mg). 1H


Hz, 2H), 4.70 (s, 2H), 3.11 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm):

δ 146.4, 132.4, 127.1, 119.0, 111.1, 64.3.

H

OH

Cl

H

OB O

O

Br

H

OH

Br

H

OB O

O

NC

H

OH

NC

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4,4,5,5-Tetramethyl-2-((4-nitrobenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 9b).2,3 1H NMR

(400 MHz, CDCl3, ppm): δ 8.18 (d, J = 8 Hz, 2H), 7.49 (d, J = 8 Hz,

2H), 5.01 (s, 2H), 1.26 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ

22.4.

(4-Nitrophenyl)methanol (9c).2,9 Brown crystalline solid. Yield: 70% (107 mg). 1H NMR

(400 MHz, CDCl3, ppm): δ 8.19 (d, J = 8 Hz, 2H), 7.52 (d, J = 8 Hz, 2H),

4.82 (s, 2H), 2.25 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 148.3,

147.4, 127.1, 123.9, 64.1.

2-((3-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 10b).2,6 1H

NMR (400 MHz, CDCl3, ppm): δ 7.54 (br, 1H), 7.41 (d, J = 8 Hz, 1H),

7.27 (d, J = 8 Hz, 1H), 7.23-7.19 (m, 1H), 4.91 (s, 2H), 1.29 (s, 12H). 11B


(3-Bromophenyl)methanol (10c).2,8 Colourless oil. Yield: 76% (142 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.46 (br, 1H), 7.41-7.39 (m, 1H), 7.21-7.20 (m, 2H),

4.54 (s, 2H), 3.65 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 143.2,

130.7, 130.2, 130.0, 125.4, 122.7, 64.4.

4,4,5,5-Tetramethyl-2-((2-methylbenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 11b).2,10 1H

NMR (400 MHz, CDCl3, ppm): δ 7.46 (br, 1H), 7.24-7.21 (m, 3H), 4.99

(s, 2H), 2.37 (s, 3H), 1.33 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ

22.4.O

HH

B OO

H

OB O

O

O2N

H

OH

O2N

H

OB O

O

Br

H

OH

Br

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o-Tolylmethanol (11c).2,7 Colourless oil. Yield: 84% (103 mg). 1H NMR (400 MHz, CDCl3, ppm): δ 7.39-7.37 (m, 1H), 7.26-7.22 (m, 3H), 4.68 (s, 2H), 2.38 (s, 4H). 13C

NMR (100 MHz, CDCl3, ppm): δ 138.8, 136.2, 130.4, 127.9, 127.6, 126.2,

63.5, 18.7.

4,4,5,5-Tetramethyl-2-(naphthalen-1-ylmethoxy)-1,3,2-dioxaborolane (Table 2, 12b).2,3 1H NMR (400 MHz, CDCl3, ppm): δ 8.19-8.16 (m, 1H), 7.99-7.90 (m, 1H),

7.73-7.71 (m, 1H), 7.64-7.55 (m, 3H), 5.54 (s, 2H), 1.40 (s, 12H). 11B NMR

(128 MHz, CDCl3, ppm): δ 22.5.

Naphthalen-2-ylmethanol (12c).2,11 Colourless oil. Yield: 87% (138 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 8.12-8.10 (m, 1H), 7.93-7.91 (m, 1H), 7.85-7.83 (m,

1H), 7.58-7.45 (m, 4H), 5.10 (s, 2H), 2.40 (br, 1H). 13C NMR (100 MHz,

CDCl3, ppm): δ 136.3, 133.8, 131.3, 128.7, 128.6, 126.4, 125.9, 125.5, 125.4,

123.7, 63.6.

2-(Furan-2-ylmethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 13b).2,6 1H

NMR (400 MHz, CDCl3, ppm): δ 7.38 (br, 1H), 6.32 (br, 2H), 4.83

(s, 2H), 1.27 (s, 12H). 13C NMR (100 MHz, CDCl3, ppm): δ 152.5,

142.4, 110.3, 108.3, 83.1, 59.2, 24.6. 11B NMR (128 MHz, CDCl3,

ppm): δ 22.4.

2-(Cinnamyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 14b).2,6 1H NMR (400

MHz, CDCl3, ppm): δ 7.47-7.38 (m, 2H), 7.34-7.30 (m, 2H), 7.26-

7.24 (m, 1H), 6.64 (d, J = 16 Hz, 1H), 6.31 (dt, J = 16, 6 Hz, 1H),

4.56 (d, J = 6 Hz, 2H), 1.29 (s, 12H). 11B NMR (128 MHz, CDCl3,

ppm): δ 22.2.

H

OH

HOB

OO

HHO

O

H

B O

O

O

H

BO

OO

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3-Phenyl-2-propene-1-ol (14c).2,12 Colourless oil. Yield: 69% (93 mg). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.43-7.41 (m, 2H), 7.37-7.33 (m, 2H), 7.30-7.28 (m,

1H), 6.64 (d, J = 16 Hz, 1H), 6.39 (dt, J = 16, 6 Hz, 1H), 4.35 (d, J = 6

Hz, 2H), 1.88 (br, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 136.8,

131.3, 128.7, 128.6, 127.8, 126.6, 63.9.

1,3-bis(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)benzene (Table 2,

15b).2,3 1H NMR (400 MHz, CDCl3, ppm): δ 7.34-7.25 (m, 4H),

4.92 (s, 4H), 1.26 (s, 24H). 11B NMR (128 MHz, CDCl3, ppm):

δ 22.3.

2-(Decyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 16b).2,4 1H NMR (400

MHz, CDCl3, ppm): δ 3.84 (t, J = 7 Hz, 2H), 1.59-1.55 (m, 2H), 1.26 (br,

26H), 0.89 (t, J = 7 Hz, 3H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.1.

Decan-1-ol (16c).2,4 Colorless oil. Yield: 54% (84 mg). 1H NMR (400 MHz, CDCl3, ppm): δ

3.59 (t, J = 6 Hz, 2H), 2.16 (br, 1H), 1.55-1.50 (m, 2H), 1.26-1.24 (m,

14H), 0.85 (t, J = 6 Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 63.0,

32.9, 32.0, 29.7, 29.7, 29.6, 29.4, 25.9, 22.8, 14.2.

4,4,5,5-Tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane (Table 3, 17b).2,3 1H NMR

(400 MHz, CDCl3, ppm): δ 7.44-7.35 (m, 4H), 7.23-7.19 (m, 1H),

5.18 (q, J = 6 Hz, 1H), 1.42 (d, J = 8 Hz, 3H), 1.14 (s, 6H), 1.13 (s,

6H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.1.

OH

H

H

OB O

O

H

OBO

O

OB O

O

H

OBpin

7

H

OH

7

S20

1-Phenylethanol (17c).2,4 Colourless oil. Yield: 70% (85 mg). 1H NMR (400 MHz, CDCl3,

ppm): δ 7.30-7.25 (m, 4H), 7.23-7.15 (m, 1H), 4.85 (q, J = 7 Hz, 1H), 2.08 (br

s, 1H), 1.46 (d, J = 7 Hz, 3H). 13C NMR (100 MHz, CDCl3): δ 145.9, 128.6,

127.6, 125.5, 70.5, 25.3.

4,4,5,5-Tetramethyl-2-(1-(p-tolyl)ethoxy)-1,3,2-dioxaborolane (Table 3, 18b).2,3 1H NMR

(400 MHz, CDCl3, ppm): δ 7.28 (d, J = 8 Hz, 2H), 7.15 (d, J = 8 Hz,

2H), 5.25 (q, J = 6 Hz, 1H), 2.35 (s, 3H), 1.50 (d, J = 8 Hz, 3H), 1.29

(s, 6H), 1.27 (s, 6H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.2.

1-(p-Tolyl)ethanol (18c).2,4 Colourless oil. Yield: 58% (79 mg). 1H NMR (400 MHz, CDCl3,

ppm): δ 7.29 (d, J = 6.4 Hz, 2H), 7.18 (d, J = 6.5 Hz, 2H), 4.87 (q, J = 6

Hz, 1H), 2.37 (s, 3H), 1.90 (s, 1H), 1.50 (d, J = 8 Hz, 3H). 13C NMR (100

MHz, CDCl3, ppm): δ 143.0, 137.3, 129.3, 125.5, 70.4, 25.2, 21.2.

2-(1-(4-Methoxyphenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3,

19b).2,3 1H NMR (400 MHz, CDCl3, ppm): δ 7.31 (d, J = 8 Hz,

2H), 6.87 (d, J = 8 Hz, 2H), 5.23 (q, J = 6 Hz, 1H), 3.80 (s, 3H),

1.50 (d, J = 4 Hz, 3H), 1.26 (s, 6H), 1.23 (s, 6H). 11B NMR (128

MHz, CDCl3, ppm): δ 22.2.

1-(4-Methoxyphenyl)ethanol (Table 3, 19c).2 Colorless oil. Yield: 61% (92 mg). 1H NMR

(400 MHz, CDCl3, ppm): δ 7.21 (d, J = 8 Hz, 2H, ArH), 6.80 (d, J = 8 Hz,

2H, ArH), 4.73 (q, J = 6.4 Hz, 1H, OCH), 3.72 (s, 3H, OCH3), 2.80 (s, 1H,

OH), 1.38 (d, J = 4 Hz, 2H, CH3). 13C NMR (100 MHz, CDCl3, ppm): δ

158.7, 138.1, 126.6, 113.7, 69.7, 55.2, 25.0.

OH

OB O

O

OH

OB O

O

MeO

OH

MeO

S21

2-(Benzhydryloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 20b).2,6 1H NMR

(400 MHz, CDCl3, ppm): δ 7.54-7.52 (m, 4H), 7.45-7.41 (m, 4H), 7.37-

7.35 (m, 2H), 6.33 (s, 1H), 1.34 (s, 12H). 11B NMR (128 MHz, CDCl3,

ppm): δ 22.3.

Diphenylmethanol (Table 3, 20c).2 White solid. Yield-: 71% (129 mg). 1H NMR (400 MHz,

CDCl3, ppm): δ 7.38-7.23 (m, 10H), 5.82 (s, 1H), 2.33 (br, 1H). 13C NMR

(100 MHz, CDCl3, ppm): δ 143.9, 128.6, 127.7, 126.7, 76.4.

2-((4-Fluorophenyl)(phenyl)methoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3,

21b). 1H NMR (400 MHz, CDCl3, ppm): δ 7.45-7.40 (m, 5H), 7.38-

7.31 (m, 2H), 7.08-7.03 (m, 2H), 6.25 (s, 1H), 1.28 (s, 12H). 11B NMR

(128 MHz, CDCl3, ppm): δ 22.4.

(4-Fluorophenyl)(phenyl)methanol (21c). White solid. Yield: 72% (144 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.36-7.29 (m, 7H), 7.04-7.0 (m, 2H), 5.79 (s,

1H), 2.58 (s, 1H). 13C NMR (100 MHz, CDCl3, ppm): δ 162.3 (d, J =

245.9 Hz), 143.7, 139.6, 128.6, 128.3 (d, J = 8 Hz), 127.8, 126.5, 115.4

(d, J = 21 Hz), 75.6.

2-(1-(4-Fluorophenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 22b).2,12 1H NMR (400 MHz, CDCl3, ppm): δ 7.37 (d, J = 8 Hz, 2H), 7.30 (d, J

= 8 Hz, 2H), 5.37 (q, J = 6 Hz, 1H), 1.61 (d, J = 8 Hz, 3H), 1.37 (s,

6H), 1.34 (s, 6H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.1.

OB O

O

OB O

O

F

OH

F

OB O

O

F

OH

S22

1-(4-Fluorophenyl)ethanol (22c).2,12 Colorless oil. Yield: 62% (87 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.36-7.34 (m, 2H), 7.07-7.02 (m, 2H), 4.90 (q, J = 6

Hz, 1H), 2.07 (s, 1H), 1.49 (d, J = 6.5 Hz, 3H). 13C NMR (100 MHz,

CDCl3, ppm): δ 162.2 (d, J = 245 Hz), 141.6, 127.2 (d, J = 8 Hz), 115.4 (d,

J = 21 Hz), 69.9, 25.4. 19F NMR (376 MHz, CDCl3, ppm): -115.33.

2-(1-(4-Bromophenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 23b).2,3

1H NMR (400 MHz, CDCl3, ppm): δ 7.42 (d, J = 8 Hz, 2H), 7.40 (d,

J = 8 Hz, 2H), 5.39 (q, J = 6.4 Hz, 1H), 1.64 (d, J = 8 Hz, 3H), 1.42

(s, 6H), 1.39 (s, 6H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.4.

1-(4-Bromophenyl)ethanol (23c).2,10 Colourless oil. Yield: 82% (164 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.47 (d, J = 8 Hz, 2H), 7.24 (d, J = 8 Hz, 2H), 4.85

(q, J = 6.4 Hz, 1H), 2.33 (s, 1H), 1.47 (d, J = 6.5 Hz, 3H). 13C NMR (100

MHz, CDCl3, ppm): δ 144.9, 131.7, 127.3, 121.3, 69.9, 25.4.

2-(2-Chloro-1-phenylethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 24b).2,14 1H NMR (400 MHz, CDCl3, ppm): δ 7.42-7.34 (m, 5H), 5.29 (m, 1H),

3.67 (m, 2H), 1.28 (s, 6H), 1.25 (s, 6H, CH3). 11B NMR (128 MHz,


2-Chloro-1-phenylethan-1-ol (24c).2,15 Colorless oil. Yield: 35% (54 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.39-7.34 (m, 5H), 4.88 (dt, J = 9, 3.3 Hz, 1H), 3.73

(dd, J = 11.3, 3.6 Hz, 1H), 3.64 (dd, J = 11.3, 8.6 Hz, 1H), 2.95 (s, 1H). 13C

NMR (100 MHz, CDCl3, ppm): δ 140.5, 129.2, 128.9, 126.6, 74.5, 51.3.

OB O

O

Br

OH

Br

OH

F

CH2Cl

OB O

O

CH2Cl

OH

S23

4,4,5,5-Tetramethyl-2-(1-(3-nitrophenyl)ethoxy)-1,3,2-dioxaborolane (Table 3, 25b).2 1H

NMR (400 MHz, CDCl3, ppm): δ 8.20 (s, 1H), 8.09-8.07 (m, 1H), 7.69-

7.67 (m, 1H), 7.50-7.46 (m, 1H), 5.30 (q, J = 6.4 Hz, 1H), 1.50 (d, J = 6.5

Hz, 3H), 1.24 (s, 6H), 1.20 (s, 6H). 11B NMR (128 MHz, CDCl3, ppm): δ

22.3.

1-(3-Nitrophenyl)ethanol (25c).2 Brown solid. Yield: 48% (79 mg). 1H NMR (400 MHz,

CDCl3, ppm): δ 8.23 (s, 1H), 8.10 (d, J = 8 Hz, 1H), 7.70 (d, J = 8 Hz, 1H),

7.50 (t, J = 8 Hz, 1H), 5.0 (q, J = 6.4 Hz, 1H), 2.37 (s, 1H), 1.52 (d, J = 6.5

Hz, 3H). 13C NMR (100 MHz, CDCl3, ppm): δ 148.4, 148.0, 131.7, 129.5,

122.4, 120.5, 69.4, 25.5.

2-(1-(2-Methoxyphenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 26b).2 1H NMR (400 MHz, CDCl3, ppm): δ 7.55 (d, J = 8 Hz, 1H), 7.25-7.21

(m, 1H), 6.99-6.95 (m, 1H), 6.84 (d, J = 8 Hz, 1H), 5.59 (q, J = 6.3 Hz,

1H), 3.83 (s, 3H), 1.46 (d, J = 6 Hz, 3H), 1.27 (s, 6H), 1.24 (s, 6H). 11B


1-(2-Methoxyphenyl)ethanol (26c).2,16 Colorless oil. Yield: 52% (78 mg). 1H NMR (400

MHz, CDCl3, ppm): δ 7.37 (m, 1H), 7.28 (m, 1H), 6.99 (m, 1H), 6.91 (m,

1H), 5.13 (q, J = 6 Hz, 1H), 3.88 (s, 3H), 2.87 (s, 1H), 1.53 (d, J = 6.5 Hz,

3H). 13C NMR (100 MHz, CDCl3, ppm): δ 156.5, 133.5, 128.3, 126.1,

120.8, 110.5, 66.4, 55.3, 23.0.

OB O

O

OMe

OH

OMe

OB O

O

NO2

OH

NO2

S24

2-(Cyclohexyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 27b).17 1H NMR

(400 MHz, CDCl3, ppm): δ 3.96 (m, 1H), 1.27-1.82 (m, 10H), 1.22 (s,

12H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.0. 13C NMR (100 MHz,

CDCl3): δ 82.5, 72.7, 34.3, 25.5, 24.6, 23.8.

2-(Adamantan-2-yloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 28b).17 1H

NMR (400 MHz, CDCl3, ppm): δ 4.17 (m, 1H), 2.13-1.41 (m, 14H),

1.23 (s, 12H). 11B NMR (128 MHz, CDCl3, ppm): δ 22.0.

2-Adamantanol (28c). White solid. Yield: 64% (96 mg). 1H NMR (400 MHz, CDCl3, ppm):

δ 3.86 (br, 1H), 2.07-2.04 (m, 2H), 1.87-1.78 (m, 7H), 1.70-1.67 (m, 4H),

1.52-1.49 (m, 2H). 13C NMR (100 MHz, CDCl3, ppm): δ 74.7, 37.7, 36.6,

34.7, 31.1, 27.6, 27.2.

OB O

O

OBO

O

OH

S25

IV. NMR Spectra of Hydroboration Products and Relevant Alcohols

Note: The borate esters spectra are shown along with internal standard (IS) nitromethane.

Resonances are denoted as follows: unreacted aldehydic or ketonic compound (*), and

solvent/grease (#).

2-(Benzyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 1b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.1

2

2.00

4.64

1.30

4.96

7.29

7.30

7.31

7.31

7.35

7.36

7.37

7.38

O

HH

B O

O

CH3

CH3 CH3

CH3

1H NMR of 1b (400 MHz, CDCl3)

-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.4

1

O

HH

B O

O

CH3

CH3 CH3

CH3

11B NMR of 1b (128 MHz, CDCl3)

S26

Phenylmethanol (1c).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.95

2.00

4.81

2.78

4.65

7.32

7.33

7.33

7.34

7.34

7.34

7.36

7.36

7.37

7.39

7.39

OH

HH

##

1H NMR of 1c (400 MHz, CDCl3)

0102030405060708090100110120130140150160170180190200f1 (ppm)

65.3

8

76.8

477

.16

77.4

8

127.

1112

7.74

128.

66

140.

96

H

OH

13C NMR of 1c (100 MHz, CDCl3)

S27

4,4,5,5-Tetramethyl-2-((4-methylbenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 2b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.3

0

3.17

2.00

1.91

2.09

1.32

2.39

4.94

7.19

7.21

7.29

7.31

IS

##

H

OB

O

O

CH3CH3

CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.2

6

H

OB

O

O

CH3CH3

CH3

CH3

CH3


S28

p-Tolylmethanol (2c).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.85

3.02

2.00

1.80

1.97

2.09

2.33

4.58

7.13

7.15

7.20

7.22

#

H

OH

CH3


0102030405060708090100110120130140150160170180190200f1 (ppm)

21.2

3

65.2

2

76.8

477

.16

77.4

8

127.

2012

9.30

137.

4113

8.01

H

OH

CH3


S29

2-((4-Methoxybenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 3b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.1

5

3.12

2.00

1.96

2.04

1.31

3.84

4.90

6.90

6.93

7.32

7.34

IS

H

OB

O

O

CH3CH3

CH3

CH3

O

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

8

H

OB

O

O

CH3CH3

CH3

CH3

O

CH3


S30

(4-Methoxyphenyl)methanol (3c).2,5

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.90

3.02

2.00

1.92

1.90

2.79

3.80

4.56

6.88

6.90

7.25

7.28

#

H

OH

O

CH3


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

55.2

8

64.7

1

76.8

477

.16

77.4

8

113.

90

128.

6513

3.21

159.

08

H

OH

OCH3


S31

4-(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)phenol (Table 2, 4b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.3

6

2.00

2.17

2.14

1.26

4.82

6.79

6.81

7.16

7.18

IS

#

#

#* * *

O

HH

B O

O

CH3

CH3 CH3

CH3

OH


-55-50-45-40-35-30-25-20-15-10-505101520253035404550556065707580859095f1 (ppm)

22.2

2

O

HH

B O

O

CH3

CH3 CH3

CH3

OH


S32

2-((4-Fluorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 5b).2,8

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.2

6

2.00

1.73

1.87

1.27

4.89

7.00

7.02

7.04

7.04

7.31

7.32

7.33

7.35

IS

#

O

HH

B O

O

CH3

CH3 CH3

CH3

F


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

5

O

HH

B O

O

CH3

CH3 CH3

CH3

F


S33

(4–Fluorophenyl)methanol (5c).2,5

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.93

2.00

1.87

1.91

2.70

4.60

7.02

7.04

7.06

7.29

7.30

7.31

7.32

# #

OH

HH

F


0102030405060708090100110120130140150160170180190200f1 (ppm)

64.5

6

76.8

477

.16

77.4

8

115.

3311

5.55

128.

81

136.

68

161.

1616

3.60

H

OH

F


S34

-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-114

.91

H

OH

F

19F NMR of 5c (376 MHz, CDCl3)

S35

2-((4-Chlorobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 6b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.4

6

2.00

1.71

1.81

1.29

4.91

7.02

7.04

7.06

7.07

7.33

7.35

7.35

7.37

O

HH

B O

O

CH3

CH3 CH3

CH3

Cl

IS

#


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.1

4

O

HH

B O

O

CH3

CH3 CH3

CH3

Cl


S36

(4–Chlorophenyl)methanol (6c).2,8

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.00

2.00

1.81

1.96

3.07

4.57

7.22

7.24

7.30

7.32

##

#

H

OH

Cl


0102030405060708090100110120130140150160170180190200f1 (ppm)

64.3

3

76.8

477

.16

77.4

8

128.

3212

8.68

133.

3213

9.29


S37

2-((4-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 7b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.1

7

2.00

2.00

1.99

1.30

4.90

7.25

7.27

7.48

7.50

IS

##

#

H

OB

O

O

CH3CH3

CH3

CH3

Br


-55-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

7

H

OB

O

O

CH3CH3

CH3

CH3

Br

S38

11B NMR of 7b (128 MHz, CDCl3)(4–Bromophenyl)methanol (7c).2,5

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.94

2.00

1.94

1.94

3.32

4.52

7.14

7.16

7.44

7.46

#

# #

H

OH

Br


S39

-100102030405060708090100110120130140150160170180190200210f1 (ppm)

64.7

5

121.

8412

9.05

132.

04

140.

17

Br

H

OH

13 C NMR of 7c (100 MHz, CDCl3)

4-(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)benzonitrile (Table 2, 8b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

11.9

1

2.00

1.95

2.06

1.27

4.99

7.45

7.47

7.62

7.64

IS

##

H

OB

O

O

CH3CH3

CH3

CH3

N

S40


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

3

H

OB

O

O

CH3CH3

CH3

CH3

N

11B NMR of 8b (128 MHz, CDCl3)4-(Hydroxymethyl)benzonitrile (8c).2,8

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.74

2.00

1.95

1.96

3.11

4.70

7.26

7.41

7.43

7.56

7.58

##

H

OH

H

N

S41


0102030405060708090100110120130140150160170180190200f1 (ppm)

64.2

6

76.8

477

.16

77.4

8

111.

17

118.

98

127.

13

132.

42

146.

42

#

H

OH

N

13C NMR of 8c (100 MHz, CDCl3)4,4,5,5-Tetramethyl-2-((4-nitrobenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 9b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

11.8

6

2.00

1.94

1.88

1.26

5.01

7.48

7.49

7.51

8.17

8.19

O

HH

B O

O

CH3

CH3 CH3

CH3

N+O

O-

IS#


S42

-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

8

O

HH

B O

O

CH3

CH3 CH3

CH3

N+O

O-


(4-Nitrophenyl)methanol (9c).2,9

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.97

2.00

1.93

1.90

2.25

4.82

7.26

7.51

7.53

8.18

8.20

#

###

H

OH

N+O

O-


S43

0102030405060708090100110120130140150160170180190200f1 (ppm)

64.1

2

76.8

477

.16

77.4

8

123.

8612

7.13

147.

4214

8.33

H

OH

N+O

O-


S44

2-((3-Bromobenzyl)oxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 10b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.0

2

2.00

1.15

1.26

0.79

0.83

1.29

4.91

7.19

7.21

7.23

7.26

7.28

7.40

7.42

7.54

IS

# #

O

HH

B O

O

CH3

CH3 CH3

CH3

Br


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

4

H

OB

O

O

CH3CH3

CH3

CH3

Br


S45

(3-Bromophenyl)methanol (10c).2,8

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.87

2.00

1.74

0.87

0.87

3.65

4.54

7.20

7.20

7.20

7.21

7.21

7.39

7.40

7.40

7.40

7.41

7.41

7.46

7.46

##

H

OH

Br


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

64.4

2

76.8

477

.16

77.4

8

122.

7112

5.43

129.

9613

0.21

130.

70

143.

18

H

OH

Br

13 C NMR of 10c (100 MHz, CDCl3)

S46

4,4,5,5-Tetramethyl-2-((2-methylbenzyl)oxy)-1,3,2-dioxaborolane (Table 2, 11b).2,10

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.2

0

2.98

2.00

2.76

0.94

1.33

2.37

4.99

7.21

7.24

7.24

7.46

IS

#

O

HH

B O

O

CH3

CH3 CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

8

O

HH

B O

O

CH3

CH3 CH3

CH3

CH3


S47

o-Tolylmethanol (11c).2,7

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

4.05

2.00

2.87

0.94

2.38

4.68

7.22

7.22

7.23

7.24

7.25

7.26

7.26

7.37

7.37

7.38

7.38

7.38

7.38

7.39

H

OH

CH3

#


0102030405060708090100110120130140150160170180190200f1 (ppm)

18.7

4

63.5

4

76.8

477

.16

77.4

8

126.

1512

7.64

127.

8813

0.42

136.

2013

8.77

#

H

OH

CH3

13 C NMR of 11c (100 MHz, CDCl3) # = grease.

S48

4,4,5,5-Tetramethyl-2-(naphthalen-1-ylmethoxy)-1,3,2-dioxaborolane (Table 2, 12b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

12.0

0

2.00

3.02

0.96

0.98

0.97

1.00

1.40

5.54

7.55

7.57

7.59

7.60

7.60

7.61

7.62

7.62

7.63

7.63

7.64

7.71

7.73

7.90

7.92

7.97

7.97

7.99

8.16

8.18

8.19

IS

#

##

HO

BOO

CH3 CH3 CH3CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.4

5

HO

BOO

CH3 CH3 CH3CH3


S49

Naphthalen-2-ylmethanol (12c).2,11

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.511.512.513.5f1 (ppm)

0.84

2.00

3.72

0.91

0.91

0.93

2.40

5.10

7.45

7.46

7.48

7.50

7.52

7.55

7.55

7.56

7.57

7.58

7.83

7.85

7.91

7.91

7.93

8.10

8.12

8.12

##

HOH


0102030405060708090100110120130140150160170180190200f1 (ppm)

63.6

0

76.8

477

.16

77.4

8

123.

7212

5.37

125.

4812

5.94

126.

4012

8.60

128.

7413

1.28

133.

8513

6.34

OH H


S50

2-(Furan-2-ylmethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 13b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.8

0

2.00

1.64

0.69

1.27

4.83

6.31

6.32

6.32

6.33

7.38

7.38

IS

##

O

H

OB

O

OCH3

CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

6

O

H

OB

O

OCH3

CH3

CH3

CH3


S51

2-(Cinnamyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 14b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.012.5f1 (ppm)

12.2

1

2.00

0.97

0.95

1.03

2.12

2.12

1.29

4.55

4.56

6.27

6.29

6.30

6.31

6.33

6.34

6.62

6.66

7.24

7.26

7.30

7.32

7.34

7.38

7.40

7.44

7.46

7.47

#

#

IS

*

#

O

H

BO

O

CH3

CH3

CH3 CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.2

4

O

H

BO

O

CH3

CH3

CH3 CH3


S52

3-Phenyl-2-propene-1-ol (14c).2,12

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.13

2.00

0.96

0.94

1.04

1.90

1.82

1.88

4.34

4.35

6.36

6.37

6.39

6.40

6.41

6.43

6.62

6.66

7.28

7.30

7.33

7.35

7.37

7.41

7.43

# ##

OH

H


0102030405060708090100110120130140150160170180190200f1 (ppm)

63.8

6

76.8

477

.16

77.4

8

126.

6012

7.84

128.

6312

8.73

131.

2913

6.80

OH

H


S53

1,3-bis(((4,4,5,5-Tetramethyl-1,3,2-dioxaborolan-2-yl)oxy)methyl)benzene (Table 2, 15b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)

24.4

2

4.00

4.13

1.26

4.92

7.25

7.27

7.29

7.30

7.34

###IS

H

OB

O

O

CH3CH3

CH3

CH3

H

OB

O

O

CH3 CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

4

H

OB

O

O

CH3CH3

CH3

CH3

H

OB

O

O

CH3 CH3

CH3

CH3


S54

2-(Decyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 2, 16b).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

2.30

21.4

2

1.65

1.45

1.00

0.87

0.89

0.91

1.26

1.55

1.57

1.59

3.82

3.84

3.86

IS

# ##

CH3

H

OB

O

O

CH3

CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-505101520253035404550556065707580859095f1 (ppm)

22.1

3

CH3

H

OB

O

O

CH3

CH3

CH3

CH3


S55

Decan-1-ol (16c).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

3.00

14.0

3

2.02

1.04

2.00

0.84

0.85

0.87

1.24

1.50

1.51

1.53

1.55

2.16

3.57

3.59

3.60

7.26

CH3

H

OH


05101520253035404550556065707580859095100105110115120125f1 (ppm)

14.1

9

22.7

825

.87

29.4

429

.57

29.6

829

.74

32.0

132

.86

62.9

9

76.8

477

.16

77.4

8

CH3

H

OH


S56

4,4,5,5-Tetramethyl-2-(1-phenylethoxy)-1,3,2-dioxaborolane (Table 3, 17b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.3

8

3.28

1.00

5.87

1.13

1.16

1.41

1.42

5.15

5.17

5.18

5.20

7.15

7.17

7.19

7.21

7.23

7.25

7.25

7.28

7.29

7.30

7.30

IS

#

#

**

*

CH3

OB

O

O

CH3CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.1

6

CH3

OB

O

O

CH3CH3

CH3

CH3


S57

1-Phenylethanol (17c).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.32

0.94

1.00

5.12

1.45

1.47

2.08

4.83

4.84

4.86

4.87

7.23

7.24

7.25

7.25

7.26

7.27

7.30

7.30

7.31

7.31

7.32

7.32

7.33

7.34

7.35

#

#

CH3

OH

H

#


0102030405060708090100110120130140150160170180190200f1 (ppm)

25.2

6

70.5

176

.84

77.1

677

.48

125.

5012

7.58

128.

61

145.

92

CH3

OH


S58

4,4,5,5-Tetramethyl-2-(1-(p-tolyl)ethoxy)-1,3,2-dioxaborolane (Table 3, 18b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.2

5

3.30

2.93

1.00

2.02

2.40

1.27

1.29

1.50

1.51

2.35

5.22

5.24

5.26

5.27

7.14

7.16

7.27

7.29

CH3

OB

O

O

CH3CH3

CH3

CH3

CH3

IS

#

##

#*


-90-80-70-60-50-40-30-20-100102030405060708090f1 (ppm)

22.1

6

CH3

OB

O

O

CH3CH3

CH3

CH3

CH3


S59

1-(p-Tolyl)ethanol (18c).2,4

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.30

0.94

3.05

1.00

2.02

2.13

1.49

1.50

2.13

2.37

4.85

4.86

4.88

4.90

7.17

7.19

7.27

7.29

7.29

IS

#

##

CH3

OH

CH3


0102030405060708090100110120130140150160170180190200f1 (ppm)

21.2

225

.21

70.3

976

.84

77.1

677

.48

125.

4812

9.30

137.

29

143.

00

CH3

OH

CH3


S60

2-(1-(4-Methoxyphenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 19b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

5.88

6.15

3.19

3.01

1.00

1.90

2.02

1.23

1.26

1.49

1.50

3.80

5.20

5.22

5.23

5.25

6.86

6.89

7.30

7.32

* *

IS

*#

#

*

CH3

OB

O

O

CH3CH3

CH3

CH3

O

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.2

5

CH3

OB

O

O

CH3CH3

CH3

CH3

O

CH3


S61

1-(4-Methoxyphenyl)ethanol (Table 3, 19c).2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.12

0.93

3.09

0.99

1.98

2.00

1.38

1.39

2.80

3.72

4.70

4.72

4.74

4.75

6.79

6.81

7.19

7.22

CH3

OH

O

CH3


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

25.0

1

55.2

0

69.6

876

.84

77.1

677

.48

113.

72

126.

66

138.

14

158.

76

CH3

OH

O

CH3


S62

2-(Benzhydryloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 20b).2,6

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.4

8

1.00

1.99

4.02

3.92

1.34

6.33

7.35

7.37

7.37

7.41

7.43

7.45

7.52

7.54

IS#

#

##

OB

O

O

CH3CH3

CH3

CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

3

OB

O

O

CH3CH3

CH3

CH3


S63

Diphenylmethanol (Table 3, 20c).2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.01

1.00

10.1

2

2.33

5.82

7.23

7.25

7.26

7.26

7.27

7.27

7.30

7.32

7.32

7.33

7.34

7.36

7.37

7.37

7.38

##

OH


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

76.3

776

.84

77.1

677

.48

126.

6712

7.70

128.

63

143.

91

OH


S64

2-((4-Fluorophenyl)(phenyl)methoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 21b).

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.3

1

1.00

2.19

2.56

6.52

1.28

6.25

7.03

7.06

7.08

7.31

7.33

7.36

7.38

7.40

7.41

7.42

7.43

7.43

7.45

7.45

IS

#

#

#* *

OB

O

O

CH3CH3

CH3

CH3

F


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.4

1

OB

O

O

CH3CH3

CH3

CH3

F


S65

(4-Fluorophenyl)(phenyl)methanol (21c).18

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

1.04

1.00

2.04

7.09

2.58

5.79

7.00

7.01

7.02

7.04

7.29

7.30

7.31

7.31

7.33

7.34

7.35

7.36

OH

F


0102030405060708090100110120130140150160170180190200f1 (ppm)

75.6

676

.85

77.1

677

.48

115.

2711

5.49

126.

5812

7.83

128.

3012

8.38

128.

68

139.

6514

3.75

161.

0316

3.47

OH

F


S66

2-(1-(4-Fluorophenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 22b).2,12

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.4

6

3.30

1.00

2.32

2.03

1.34

1.37

1.60

1.62

5.34

5.36

5.38

5.39

7.29

7.31

7.36

7.38

IS

#

* * **

CH3

OB

O

O

CH3CH3

CH3

CH3

F


-90-80-70-60-50-40-30-20-100102030405060708090f1 (ppm)

22.1

4

CH3

OB

O

O

CH3CH3

CH3

CH3

F


S67

1-(4-Fluorophenyl)ethanol (22c).2,12

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.24

1.03

1.00

1.92

1.94

1.48

1.50

2.07

4.87

4.89

4.91

4.92

7.02

7.05

7.07

7.34

7.35

7.36

CH3

OH

F


-100102030405060708090100110120130140150160170180190200210f1 (ppm)

25.4

0

69.8

876

.84

77.1

677

.48

115.

2611

5.48

127.

1312

7.21

141.

62

161.

0116

3.45

CH3

OH

F


S68

-180-170-160-150-140-130-120-110-100-90-80-70-60-50-40-30-20-100f1 (ppm)

-115

.33

CH3

OH

F

19F NMR of 22c (376 MHz, CDCl3)

S69

2-(1-(4-Bromophenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 23b).2,3

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.1

7

3.12

1.00

2.09

2.06

1.39

1.42

1.64

1.65

5.36

5.38

5.40

5.41

7.40

7.41

7.42

7.43

IS

#

** *

CH3

OB

O

O

CH3CH3

CH3

CH3

Br


-90-80-70-60-50-40-30-20-100102030405060708090f1 (ppm)

22.3

8

CH3

OB

O

O

CH3CH3

CH3

CH3

Br


S70

1-(4-Bromophenyl)ethanol (23c).2,10

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.04

0.97

1.00

1.91

1.94

1.46

1.47

2.33

4.82

4.84

4.85

4.87

7.23

7.25

7.46

7.49

#

CH3

OH

Br


0102030405060708090100110120130140150160170180190200f1 (ppm)

25.3

6

69.8

8

76.8

477

.16

77.4

8

121.

2712

7.27

131.

67

144.

88

CH3

OH

Br


S71

2-(2-Chloro-1-phenylethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 24b).2,14

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.3

3

1.95

1.00

5.39

1.25

1.28

3.66

3.66

3.68

5.28

5.29

5.29

5.31

7.34

7.36

7.38

7.40

7.40

7.42

IS

**

*

OB

O

O

CH3CH3

CH3

CH3

Cl


-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

4

OB

O

O

CH3CH3

CH3

CH3

Cl


S72

2-Chloro-1-phenylethan-1-ol (24c).2,15

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

0.98

1.04

1.05

1.00

4.99

2.95

3.62

3.64

3.65

3.67

3.71

3.72

3.74

3.75

4.86

4.87

4.88

4.88

4.89

4.90

7.34

7.35

7.35

7.36

7.37

7.37

7.38

7.38

7.39

##

Cl

OH


2030405060708090100110120130140150160170180190200f1 (ppm)

51.2

7

74.5

4

126.

5712

8.93

129.

15

140.

47

OH

Cl


S73

4,4,5,5-Tetramethyl-2-(1-(3-nitrophenyl)ethoxy)-1,3,2-dioxaborolane (Table 3, 25b).2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

11.9

6

3.14

1.00

1.05

1.30

1.00

1.44

1.20

1.24

1.49

1.51

5.28

5.29

5.31

5.33

7.46

7.48

7.49

7.50

7.67

7.67

7.69

7.69

8.07

8.09

8.20

8.23

8.23

8.26

8.28

IS

#

#

**

CH3

OB

O

O

CH3CH3

CH3

CH3

N+

O O-


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

22.3

1

CH3

OB

O

O

CH3CH3

CH3

CH3

N+

O O-


S74

1-(3-Nitrophenyl)ethanol (25c).2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.12

1.00

1.00

0.99

0.99

0.95

0.97

1.51

1.53

2.37

4.98

5.00

5.01

5.03

7.48

7.50

7.52

7.69

7.71

8.09

8.11

8.23

##

#

CH3

OH

N+

O O-


0102030405060708090100110120130140150160170180190200f1 (ppm)

25.5

2

69.4

2

76.8

477

.16

77.4

8

120.

4912

2.41

129.

5213

1.73

148.

0214

8.40

CH3

OH

N+

O O-

13C NMR of 25C (100 MHz, CDCl3)

S75

2-(1-(2-Methoxyphenyl)ethoxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 26b).2

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

5.81

5.69

3.11

3.03

1.00

0.85

1.34

1.15

1.01

1.24

1.27

1.45

1.47

3.83

5.57

5.58

5.60

5.62

6.83

6.85

6.95

6.97

6.99

7.21

7.23

7.24

7.25

7.54

7.56

IS

CH3

OB

O

O

CH3CH3

CH3

CH3

OCH3


-90-80-70-60-50-40-30-20-100102030405060708090f1 (ppm)

22.2

7

CH3

OB

O

O

CH3CH3

CH3

CH3

OCH3


S76

1-(2-Methoxyphenyl)ethanol (26c).2,16

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

3.11

0.93

3.17

1.00

0.95

0.96

0.98

0.96

1.52

1.54

2.87

3.88

5.10

5.12

5.13

5.15

6.90

6.92

6.97

6.99

7.01

7.26

7.28

7.30

7.37

7.38

# #

CH3

OH

OCH3


0102030405060708090100110120130140150160170180190200f1 (ppm)

22.9

6

55.3

0

66.4

4

76.8

477

.16

77.4

8

110.

46

120.

8512

6.13

128.

3213

3.54

156.

55

O

CH3

O

CH3


S77

2-(Cyclohexyloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 27b).17

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)

12.3

1

10.0

5

1.00

1.22

1.27

1.27

1.28

1.30

1.33

1.35

1.35

1.45

1.46

1.47

1.47

1.48

1.49

1.50

1.68

1.68

1.70

1.71

1.79

1.79

1.81

1.82

3.93

3.94

3.95

3.96

3.97

3.98

3.99

IS

#

#

OB

O

O

CH3

CH3

CH3CH3


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

21.9

5

OB

O

O

CH3

CH3

CH3CH3


S78

0102030405060708090100110120130140150160170180190200f1 (ppm)

23.8

524

.62

25.5

0

34.2

9

72.6

576

.84

77.1

677

.48

82.4

8

OB

O

O

CH3 CH3

CH3

CH3

13C NMR of 27b (100 MHz, CDCl3)

S79

2-(Adamantan-2-yloxy)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (Table 3, 28b).17

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

12.1

4

14.8

5

1.00

1.23

1.41

1.44

1.67

1.71

1.74

1.75

1.76

1.77

1.78

1.80

1.81

1.88

2.10

2.13

4.16

4.17

4.18

IS

#

OBpin


-50-45-40-35-30-25-20-15-10-5051015202530354045505560657075808590f1 (ppm)

21.9

4

OBpin


S80

2-Adamantanol (28c).19

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

2.20

4.30

7.18

2.17

1.00

1.49

1.50

1.52

1.67

1.70

1.78

1.79

1.80

1.81

1.82

1.86

1.86

1.87

2.04

2.07

3.86

7.26

##


05101520253035404550556065707580859095100f1 (ppm)

27.1

927

.64

31.1

4

34.6

636

.63

37.7

1

74.6

776

.84

77.1

677

.48

OH


OH

S81

V. Competitive Chemoselective Hydroboration Reactions

Experimental Procedure for the Examples Described in Scheme 2a: In a 10 mL thick-

walled reaction tube equipped with a magnetic stirring bar, Fe2O3 NPs (5 mol %, 2 mg,

0.0125 mmol), HBpin (1.0 equiv, 36 µL, 0.25 mmol), toluene (1 mL), aldehyde (0.25

mmol) and ketone (0.25 mmol) were added and the reaction was stirred vigorously at room

temperature for 8 h. The reaction mixture was then diluted with Et2O (2 mL) and filtered

through a plug of celite (∅ 3 mm × 8 mm) with copious washing (Et2O). The solvents were

removed in vacuo, and the borate esters yields were determined by 1H NMR spectroscopy

using nitromethane as an internal standard.

O

H

O

+

OBPin

H +

OBPinFe2O3 (5 mol %)HBpin (1 equiv)Toluene (1 mL)RT, 8 h

52% 26%(1 equiv) (1 equiv)

a-1)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

1.00

1.09

0.29

4.96

5.25

5.27

5.29

5.30

CH3

OB

O

O

CH3CH3

CH3

CH3

H

OB

O

O

CH3CH3

CH3

CH3

Figure S5. 1H NMR spectra of competitive hydroboration reaction between benzaldehyde

(1a) and acetophenone (17a).

S82

O

H

O

+

OBPin

H+

OBPin

30%67%(1 equiv) (1 equiv)

Fe2O3 (5 mol %)HBpin (1 equiv)Toluene (1 mL)RT, 8h

a-2)

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)

1.00

1.31

0.34

4.92

5.24

5.25

5.27

5.29

Figure S6. 1H NMR spectra of competitive hydroboration reaction between 4-

methylbenzaldehyde (2a) and 1-(p-tolyl)ethanone (18a).

S83

O

H

O

+

OBPin

H+

OBPin

F F

20%63 %F F

(1 equiv) (1 equiv)

Fe2O3 (5 mol %)HBpin (1 equiv)Toluene (1 mL)RT, 8h

a-3)

-0.50.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)

1.00

1.67

0.29

4.87

5.20

5.21

5.23

5.24

Figure S7. 1H NMR spectra of competitive hydroboration reaction between 4-

fluorobenzaldehyde (5a) and 1-(4-fluorophenyl)ethanone (22a).

S84

Experimental Procedure for the Examples Described in Scheme 2b: In a 10 mL thick-


0.0125 mmol), HBpin (1.0 equiv, 36 µL, 0.25 mmol), toluene (1 mL) and substrate (0.25

mmol) were added and the reaction was stirred vigorously at room temperature for 10 h. The

reaction mixture was then diluted with Et2O (2 mL) and filtered through a plug of celite (∅ 3

mm × 8 mm) with copious washing (Et2O). The solvents were removed in vacuo, and the

borate ester yield was determined by 1H NMR spectroscopy using nitromethane as an internal

standard.

OBpin

H

O

O

H

O

Fe2O3 (5 mol %)HBpin (1 equiv)Toluene, RT, 10 h

29a 29b: 97%

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.011.512.0f1 (ppm)

12.3

5

3.18

2.00

2.00

2.23

1.29

2.60

5.01

7.44

7.46

7.94

7.96

#

H

OB

O

O

CH3CH3

CH3

CH3

CH3

O

IS

*

Figure S8. 1H NMR spectra of intramolecular competitive hydroboration reaction of 4-acetylbenzaldehyde (29a).

S85


O

H

O

O

OBpin

H

O

O

30b: 93%30a

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

12.8

9

3.18

2.00

1.96

1.96

1.31

2.32

4.96

7.09

7.11

7.39

7.41

IS#

H

OB

O

O

CH3CH3

CH3

CH3

OCH3

O

Figure S9. 1H NMR spectra of intramolecular competitive hydroboration reaction of 4-

formylphenyl acetate (30a).

S86

O

H

N

O

OBpin

H

NH

O

H 31b: 79%


31a

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)

11.7

4

4.01

2.00

2.28

1.88

0.92

1.27

2.11

4.87

7.24

7.26

7.48

7.50

8.43

IS

# #

*

H

OB

O

O

CH3CH3

CH3

CH3

NCH3

O

H

Figure S10. 1H NMR spectra of intramolecular competitive hydroboration reaction of N-(4-

formylphenyl)acetamide (31a).

S87

Experimental Procedure for the Example Described in Scheme 2c: In a 10 mL thick-


0.0125 mmol), HBpin (1.2 equiv, 44 µL, 0.3 mmol), toluene (1 mL), benzaldehyde (0.25

mmol), 4-methoxybenzaldehyde (0.25 mmol) and fluorobenzaldehyde (0.25 mmol) were

added and the reaction was stirred vigorously at room temperature for 8 h. The reaction

mixture was then diluted with Et2O (2 mL) and filtered through a plug of celite (∅ 3 mm × 8

mm) with copious washing (Et2O). The solvents were removed in vacuo, and the borate esters

yields were determined by 1H NMR spectroscopy using nitromethane as an internal standard.

0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.511.0f1 (ppm)

1.00

0.40

0.77

0.94

4.85

4.88

4.93

F

H

OBpin

O

H

OBpin

CH3

H

OBpin

4.74.84.95.05.15.2f1 (ppm)

0.40

0.77

0.94

4.85

4.88

4.93

Figure S11. 1H NMR spectra of competitive hydroboration reaction between benzaldehyde

(1a), 4-methoxybenzaldehyde (3a) and 4-fluorobenzaldehyde (5a).

S88

VI. Mechanistic Investigations

Mercury Poisoning Experiments.a) In a 10 mL thick-walled reaction tube equipped with a magnetic stirring bar, Fe2O3 NPs

(5 mol %, 2 mg, 0.0125 mmol), HBpin (1.2 equiv, 44 µL, 0.3 mmol), toluene (1 mL),

benzaldehyde (0.25 mmol, 20 μL) and Hg (300 equiv) were added and the reaction was

stirred vigorously at room temperature for 8 h. The reaction mixture was then diluted with

Et2O (2 mL) and filtered through a plug of celite (∅ 3 mm × 8 mm) with copious washing

(Et2O). The solvents were removed in vacuo, and the borate ester yield was determined by 1H NMR spectroscopy using nitromethane as an internal standard, no isolable product was

obtained in this experiment.

+Fe2O3 (5 mol%)O

H

O

H

Bpin

HToluene (1mL)Hg (300 equiv)RT, 8 h

1b: 0%

HBpin

(1.2 equiv)1a

b) In a 10 mL thick-walled reaction tube equipped with a magnetic stirring bar, Fe2O3 NPs

(5 mol %, 2 mg, 0.0125 mmol), HBpin (1.2 equiv, 44 µL, 0.3 mmol), toluene (1 mL) and

benzaldehyde (0.25 mmol, 20 μL) were added, and the reaction was stirred vigorously at

room temperature for 1 h. After 1 h reaction process, the reaction was interrupted and 300

equiv of Hg was added. After stirring for about 8 h at room temperature the reaction

mixture was then diluted with Et2O (2 mL) and filtered through a plug of celite (∅ 3 mm ×

8 mm) with copious washing (Et2O). The solvents were removed in vacuo, and the borate

ester yield was determined by 1H NMR spectroscopy using nitromethane as an internal

standard.

+

i) Fe2O3 (5 mol%)Toluene (1mL)RT, 1 h

O

H

O

H

Bpin

H

1b: 33%

HBpin

(1.2 equiv)1a

ii) Hg (300 equiv)RT, 8 h

S89

Recyclability Experiment for Hydroboration of 4-bromobenzaldehyde (7a).

O

H

OBpin

HFe2O3 (5 mol %)HBpin (1.2 equiv)Toluene, RT, 12hBr Br

1 mmol7a

7b

In a 50 mL round bottom flask equipped with a magnetic stirring bar, 5 mol% of Fe2O3 (5

mol %, 0.05 mmol, 8 mg), HBpin (1.2 mmol, 174 μL), toluene (4 mL) and 4-

bromobenzaldehyde (7a, 1.0 mmol, 185 mg) were added. The resulting reaction mixture was

stirred vigorously at room temperature for 12 h. After completion of the reaction, the solid

was centrifuged out of suspension and extracted with diethyl ether (three times). The solvents

were removed in vacuo, and the combined organic extracts were analyzed by 1H NMR

spectroscopy using nitromethane as an internal standard.

The recovered Fe2O3 NPs was charged into 50 mL round bottom flask equipped with

a magnetic stirring bar, to which additional HBpin (1.2 mmol, 174 μL), toluene (4 mL) and 4-

bromobenzaldehyde (1.0 mmol, 185 mg) were added. The resulting reaction mixture was

stirred vigorously at room temperature for 12 h. Then, NPs were centrifuged out of

suspension and extracted with Et2O. The combined organic product was extracted five times

with Et2O after each run and the reaction was continued with a fresh batch of substrate (4-

bromobenzaldehyde, 1 mmol scale), HBpin(1.2 mmol, 174 μL) and toluene (4 mL) added to

the separated Fe2O3 NPs. The combined organic extracts were analyzed by 1H NMR

spectroscopy using nitromethane as an internal standard. The results of 5 recycling

experiments are summarized in Figure S12.

Yields: 1st cycle = 99%, 2nd cycle = 99%, 3rd cycle = 94%, 4th cycle = 89 %, 5th cycle = 52%.

Gratifyingly, when the recovered catalyst, after the fifth cycle of the reaction, was

calcined at 500 °C for 3 h, and has been used as a catalyst for the hydroboration of 4-

S90

bromobenzaldehyde (7a) under standard reaction conditions gave the desire borate ester 7b in

99% yield confirmed by 1H NMR spectroscopy.

Figure S12.1H NMR yields (%) of borate ester at different cycles in the recyclability experiment for Fe2O3 NPs catalysed hydroboration of 4-bromobenzaldehyde.

Figure S13. TEM images of Fe2O3 nanoparticles after 5 reuses.

The nanoparticles recovered after 5 reuses were characterized by transmission electron

microscopy (TEM). The TEM images demonstrated that the nanoparticles were having

particle size in the range of 20-65 nm and an average particle size of ∼37.8 nm.

S91

Figure S14. TEM images of calcined Fe2O3 nanoparticles, recovered after 5 catalytic cycles.

The calcined Fe2O3 nanoparticles recovered after 5 catalytic cycles were characterized by

transmission electron microscopy (TEM). The TEM images demonstrated that the

nanoparticles were having particle size in the range of 20-63 nm and an average particle size

of ∼35.7 nm.

S92

Stoichiometric reaction of Fe2O3 NPs with substrate and HBpin.

In an argon-filled glovebox, the Fe2O3 NPs (20 mg, 0.125 mmol) and benzaldehyde (13 mg,

0.125 mmol) were mixed and the reaction mixture was analyzed by fourier transform infra-

red (FT-IR) spectroscopy (Figure S15). The strong absorption peaks at 534 and 462 cm-1 can

be attributed to the Fe–O band vibrations (Figure S15-a). The strong absorption peak at 1701

cm-1 is due to the CO stretching frequency (Figure S15-b). The FT-IR spectrum of the

reaction mixture shows shift in the absorption band correspond to the Fe–O vibration as well

as in the CO stretching frequency towards lower wavenumber indicating interaction between

Fe2O3 and benzaldehyde (Figure S15-c)

(a) (b)

(c)

Figure S15. IR spectra of: (a) Fe2O3; (b) C6H5CHO and (c) Fe2O3 + C6H5CHO.

S93

In an argon-filled glovebox, the Fe2O3 NPs (20 mg, 0.125 mmol) and excess HBpin (160 mg,

1.25 mmol) were mixed and the reaction mixture was analyzed by FT-IR spectroscopy

(Figure S16). The FT-IR spectrum of the reaction mixture shows shift in the absorption band

correspond to the Fe–O vibration towards lower wavenumber indicating interaction between

Fe2O3 and HBpin (Figure S16-c)

(a) (b)

(c)

Figure S16. IR spectra of: (a) Fe2O3; (b) HBpin and (c) Fe2O3 + HBpin.

S94

VII. References

1. (a) H. Braunschweig, F. Guethlein, L. Mailander and T. B. Marder, Chem. Eur. J.,

2013, 19, 14831-14835; (b) A. K. Arora, M. Sharma, R. Kumari, V. S. Jaswal and P.

Kumar, J. Nanotechnol. 2014, DOI:10.1155/2014/474909.

2. A. Baishya, S. Baruah and K. Geetharani, Dalton Trans., 2018, 47, 9231-9236.

3. Y. Wu, C. Shan, J. Ying, J. Su, J. Zhu, L. L. Liu and Y. Zhao, Green Chem., 2017, 19,

4169-4175.

4. A. Kaithal, B. Chatterjee and C. Gunanathan, Org. Lett., 2015, 17, 4790-4793.

5. V. K. Jakhar, M. K. Barman and S. Nembenna, Org. Lett., 2016, 18, 4710-4713.

6. S. Yadav, S. Pahar and S. Sen, Chem. Commun., 2017, 53, 4562-4564.

7. T. Osako, K. Torii, S. Hirata and Y. Uozumi, ACS Catal., 2017, 7, 7371-7377.

8. T. Mandal, S. Jana and J. Dash, Eur. J. Org. Chem., 2017, 4972-4983.

9. T. Bai, T. Janes and D. Song, Dalton Trans., 2017, 46, 12408-12412.

10. S. Chen, D. Yan, M. Xue, Y. Hong, Y. Yao and Q. Shen, Org. Lett. 2017, 19, 3382-

3385.

11. S. R. Tamang and M. Findlater, J. Org. Chem., 2017, 82, 12857-12862.

12. S. R. Tamang and M. Findlater, J. Org. Chem., 2017, 82, 12857-12862.

13. H. Maeda, S. Endo, T. Ouchi, K. Mizuno and M. Segi, Chem. Lett. 2017, 46, 1357-

1360.

14. G. Zhang, H. Zeng, J. Wu, Z. Yin, S. Zheng and J. C. Fettinger, Angew. Chem. Int.

Ed., 2016, 55, 14369-14372.

15. L. S. Pimenta, E. V. Gusevskaya and E. E. Alberto, Adv. Synth. Catal., 2017, 359,

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Supporting Information hydroboration of carbonyl compounds · S1 Supporting Information Reusable...

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