Life Science Intermediates for Organic Synthesis - BASF
Transcript of Life Science Intermediates for Organic Synthesis - BASF
Life Science Intermediates for Organic SynthesisProduct Overview
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Table of Contents
Suzuki Coupling Reagents ..............................................................................................................................................1
Borane Complexes .........................................................................................................................................................1
Amine Boranes ................................................................................................................................................................1
Chiral Reagents ...............................................................................................................................................................2
Calselect® Reducing Agents ...........................................................................................................................................2
Alkylboranes....................................................................................................................................................................3
Boroxins and Borates .....................................................................................................................................................3
Alkali Metal Alcoholates ..................................................................................................................................................4
Alkali Metal Amides .........................................................................................................................................................5
Other Alkali Metal Compounds .......................................................................................................................................5
Hydroxyacetophenones and Phenyl Acetate ..................................................................................................................5
Hydroxylamine Derivatives ..............................................................................................................................................6
High Purity Iron Salts ......................................................................................................................................................6
Index ...............................................................................................................................................................................7
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Suzuki Coupling ReagentsBoronic acids and esters have become very important building blocks in organic synthesis through the Suzuki-Miyaura cross-coupling protocols. The Suzuki-Miyaura reaction1 is a powerful synthetic tool for the formation of carbon-carbon bonds, dramatically shortening multistep synthetic routes since this process easily couples large molecular fragments containing functional groups. Trialkylborane and aryldialkylborane reagents can also participate in these valuable coupling reactions.
1Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2457.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
Bis(pinacolato)diboron PIN2B2 73183-34-3 C12
H24
B2O
4
253.94Powder
Catecholborane CATB 274-07-7 C6H
5BO
2
119.92
50 wt% in toluene 0.911
Pinacolborane PINB 25015-63-8 C6H
13BO
2
128.00 Neat w/ 1% TEA 0.875
Borane ComplexesBorane complexes are versatile compounds commonly used as regio-, chemo- and stereoselective reducing agents for a variety of functional groups such as aldehydes, ketones, carboxylic acids, amides and olefins. The high yields and simple isolation of the reduced products combined with the high selectivities achieved with borane reagents have made these compounds the favorite reducing agents for a number of applications.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
Borane tetrahydrofuran complex BTHF 14044-65-6 C4H
11BO
85.941M in THF 0.878
Dimethylsulfide borane complex DMSB 13292-87-0 C2H
9BS
75.9710M in DMS2M in THF
0.7940.865
Amine BoranesComplexation of borane with a strong Lewis base, such as an unhindered amine, produces air and moisture stable amine borane complexes. The stability, solubility, and ease of handling make them attractive borane sources in many reactions where aqueous, alcoholic or acidic solvents are desirable. 5-Ethyl-2-methylpyridine borane is a new complex which is easily handled and has up to three hydrides available for reductive amination and reduction.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
2-Picoline borane PICB 3999-38-0 C7H
10BN
103.9530 wt% THF 0.909
5-Ethyl-2-methylpyridine borane PEMB 1006873-58-0 C8H
14BN
135.01Neat liquid 0.913
Dimethylamine borane DMAB 74-94-2 C2H
10BN
58.92Neat Solid 0.73 g/cc
N,N-Diethylaniline borane DEANB 13289-97-9 C10
H18
BN163.07
Neat liquid 0.921
Pyridine borane PYB 110-51-0 C5H
8BN
92.93Neat liquid 0.921
t-Butylamine borane TBAB 7337-45-3 C4H
14BN
86.97Powder 0.46 g/cc
(bulk)
Triethylamine borane TEAB 1722-26-5 C6H
18BN
115.03Neat liquid 0.782
Chiral ReagentsBoth methyl oxazaborolidine (MeCBS) and diisopinocampheylchloroborane (DPC) are excellent choices for the enantioselective reduction of prochiral ketones. While DPC is a stoichiometric reducing agent, MeCBS (Corey catalyst) is a catalyst that is typically used in conjunction with a borane source such as borane tetrahydrofuran (BTHF), dimethylsulfide borane (DMSB) or N,N-diethylaniline borane (DEANB). Both products have proven their advantages over alternative technologies in commercial applications and are available in both enantiomeric forms from BASF.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
(-)-Diisopinocampheylchloroborane (-)-DPC 85116-37-6 C20
H34
BCl320.80
60-65 wt% heptanes 0.855
(+)-Diisopinocampheylchloroborane (+)-DPC 112246-73-8 C20
H34
BCl320.80
60-65 wt% heptanes60-65 wt% hexanes
0.8550.890
(R)-Methyl oxazaborolidine (R)-MeCBS 112022-83-0 C18
H20
BNO277.17
1M in toluene 0.927
(S)-Methyl oxazaborolidine (S)-MeCBS 112022-81-8 C18
H20
BNO277.17
1M in toluene 0.927
Calselect® Reducing AgentsAlkali metal trialkylborohydrides have been used in numerous stereoselective and regioselective reductions. The strength and reactivity of these reducing agents varies with the steric bulk of the alkyl groups and the alkali metal ion. Calselect® STAB is a selective reducing agent that has proven to be extremely useful in reductive aminations.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
Lithium triethylborohydride CALSELECT® LT 22560-16-3 C6H
16BLi
105.951M in THF 0.890
Lithium tri-sec-butylborohydride CALSELECT® Li 38721-52-7 C12
H28
BLi190.11
1M in THF 0.898
Sodium triacetoxyborohydride CALSELECT® STAB 56553-60-7 C6H
10BNaO
6
211.96PowderGranular
0.765 g/cc (bulk)
Sodium tri-sec-butylborohydride CALSELECT® Na 67276-04-4 C12
H28
BNa206.15
1M in THF 0.898
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AlkylboranesAlkylboranes are versatile products used in different industrial applications such as Pharmaceuticals, Polymers and others. In organic synthesis triethylborane (TEB) and methoxydiethylborane (MDEB) have proven especially effective as diastereoselective reagents to produce syn-diols from β-hydroxyketones. Dibutylboron triflate (DBBT) is used to form boron enolates in diastereoselective aldol condensations following the Evans’ and similar protocols. BASF’s ready-to-use solution of DBBT is now available from lab scale to ton quantities as solutions in toluene.
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
9-Borabicyclo[3.3.1]nonane 9BBN 280-64-8 C8H
15B
122.020.5M in THF 0.882
Dibutylboron triflate DBBT 60669-69-4 C9H
18BF
3O
3S
274.151M in toluene 0.903
Methoxydiethylborane MDEB 7397-46-8 C5H
13BO
99.97Neat liquid50 wt% in THF
0.7490.807
Triethylborane TEB 97-94-9 C6H
15B
98.00Neat liquid14 wt% in THF
0.6960.848
Triethylborane-1,3-diaminopropane complex TEB-DAP 148861-07-8 C9H
25BN
2
172.12Neat liquid 0.859
Tri-n-butylborane TNBB 122-56-5 C12
H27
B182.16
Neat liquid 0.748
Tri-n-butylborane-3-methoxypropylamine complex TnBB-MOPA 345269-15-0 C15
H37
BN2
271.25Neat liquid 0.826
Boroxins and Borates
NameAbbreviation/ Trade Name Structure CAS#
Formula FW (g/mol) Form
Density (g/ml)
Trimethoxyboroxin TMBX 102-24-9 C3H
9B
3O
6
173.53Neat liquid 1.216
Trimethylboroxin MBX 823-96-1 C3H
9B
3O
3
125.5350 wt% in THF 0.894
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Alkali Metal AlcoholatesAlcoholates are moderately strong base reagents that are used in many drug and chemical synthesis applications, such as alkylation, arylation, acylation, solvolysis of esters, condensation, elimination, isomerization, rearrangements, transfer, hydrogenation, Wittig reactions, and redox reactions. The reactivity can be fine tuned to the desired reaction by correct choice of alcoholate and counterion. The wide range of properties and solubilities available from BASF Corporation allows for process optimization and high yields.
Potassium Alcoholates
Name/SynonymAbbreviation/ Trade Name Structure CAS #
Formula FW (g/mol) Forms
Density (g/ml)
Potassium 3,7-Dimethyl-3-octylatePotassium 3,7-Dimethyl-3-octanoxide
KDMO/Heptane 50% 263148-42-1 C10
H21
KO196.37
50% w/w in n-heptane
0.804
Potassium EthylatePotassium Ethoxide
KE 24%(DN with toluene)
917-58-8 C2H
5KO
84.1424% w/w in ethanol 0.895
Potassium MethylatePotassium Methoxide
KMKM 32% KOMe
865-33-8 CH3KO
70.14Powder32% w/w in methanol
0.978
Potassium tert.-AmylatePotassium tert.-Pentoxide
KTAKTA/Cyclohexane 15%
KTA/Toluene 25%
KTA/THF 45%
41233-93-6 C5H
11KO
126.20Powder
15% w/w in cyclohexane25% w/w in toluene
45% w/w in THF
0.57 g/cc (Bulk)
0.801
0.904
0.951 @ 21˚C
Potassium tert.-ButylatePotassium tert-Butoxide
KTBKTB/TBA 15%
KTB/THF 20%
KTB/TBA 13.7% with THF
865-47-4 C4H
9KO
112.21Powder
15% w/w in tert.-butanol20% w/w in THF
13.7% w/w in TBA with THF
0.813
0.818
0.906
0.838 @ 25˚C
Sodium Alcoholates
Name/SynonymAbbreviation/ Trade Name Structure CAS #
Formula FW (g/mol) Forms
Density (g/ml)
Sodium EthylateSodium Ethoxide
SESE 21%
141-52-6 C2H
5NaO
68.05Powder21% w/w in ethanol 0.880
Sodium Mentholate NaM/Hexanes 50% 19321-38-1 C10
H19
NaO178.25
50% w/w in hexanes 0.815
Sodium MethylateSodium Methoxide
SMSMS 25%
SMS 30%NaOMe
124-41-4 CH3NaO
54.03Powder25% w/w in methanol30% w/w in methanol
0.944
0.969
Sodium n-ButylateSodium n-Butoxide
SNB/NBA 19% 2372-45-4 C4H
9NaO
96.119% w/w in n-butanol
0.853
Sodium tert.-AmylateSodium tert.-Pentoxide
STASTA/Hexanes 38%
STA/THF 35%STA/Toluene 25%
14593-46-5 C5H
11NaO
110.13Powder38% w/w in hexanes
35% w/w in THF25% w/w in toluene
0.752
0.9260.885
Sodium tert.-ButylateSodium tert.-Butoxide
STB 865-48-5 C4H
9NaO
96.02Powder 0.698 g/cc
(Bulk)
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Alkali Metal AmidesPotassium hexamethyldisilazane (KHMDS), sodium hexamethyldisilazane (NaHMDS), and lithium hexamethyldisilazane (LiHMDS) are strong non-nucleophilic base reagents useful in a wide variety of chemical reactions and transformations. Applications include aklylation, acylation, ring formation, isomerization, rearrangements, aldol condensations, Wittig and Horner-Emmons reactions and polymerization. Their high selectivity and specificity can lead to simpler, less expensive purification routes to the desired product.
Name/SynonymAbbreviation/ Trade Name Structure CAS #
Formula FW (g/mol) Forms
Density (g/ml)
Potassium HexamethyldisilazanePotassium bi(trimethylsily)amide
KHMDS/THF 20%KHMDS/Toluene 15%
40949-94-8 C6H
18KNSi
2
199.520% w/w in THF15% w/w in toluene
0.8980.879
Lithium HexamethyldisilazaneLithium bi(trimethylsily)amide
LiHMDS/THF 24% 4039-32-1 C6H
18LiNSi
2
167.3324% w/w in THF 0.867
Sodium HexamethyldisilazaneSodium bis(trimethylsilyl)amide
NaHMDS/THF 40%NaHMDS/Toluene 13%
1070-89-9 C6H
18NNaSi
2
183.3840% w/w in THF13% w/w in toluene
0.8890.868 @ 21.0 ˚C
Other Alkali Metal CompoundsSodium-Potassium Alloy (NaK), essentially a liquid form of Potassium metal, is mainly used for reductions and as a raw material for making potassium derivatives. Potassium superoxide (KO2) has its main applications as a chemical oxygen source.
Name/SynonymAbbreviation/ Trade Name Structure CAS #
Formula FW (g/mol) Forms
Density (g/ml)
Potassium Superoxide KO2 CAT
KO2 UNCAT
KO2 UNCAT fluff
KO2
12030-88-5 KO2
Catalyzed granulesUncatalyzed granulesUncatalyzed fluff
Sodium Potassium Alloy NaK NaK 11135-81-2 NaK Liquid 0.855
Hydroxyacetophenones and Phenyl Acetate4-Hydroxyacetophenone (4-HAP) is a versatile building block for a variety of uses including semiconductors, specialty polymers, pharmaceuticals, agricultural chemicals, flavors and fragrances, cosmetic and other fine chemical applications.
Name/SynonymAbbreviation/ Trade Name Structure CAS No.
Formula FW (g/mol) Forms
Density (g/ml)
2-Hydroxyacetophenone 2-HAPOrtho-Hydroxyacetophenone
118-93-4 C8H
8O
2
136.15Liquid 1.157
Bulk
4-Hydroxyacetophenone 4-HAP1-(4-Hydroxyphenyl)ethanonep-Hydroxyacetophenonep-Hydroxyphenyl methyl ketone
99-93-4 C8H
8O
2
136.15Powder 1.157
Bulk
Phenyl Acetate PhOAc 122-79-2 C7H
14O
2
130.2Liquid 0.875-
0.877
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Hydroxylamine DerivativesBASF offers a growing range of Hydroxylamine derivatives used to introduce N-O-functionality into a molecule. Recent examples of our ongoing portfolio expansion include: Hydroxylamine-O-sulfonic acid, a versatile aminating agent; O-Benzylhydroxylamine hydrochloride, used to introduce an N-O functionality that is protected from other reactions and easily de-protected under mild conditions; and N,O-Dimethylhydroxylamine hydrochloride that makes production-scale “Weinreb-Chemistry” feasible.
Name/SynonymAbbreviation/ Trade Name Structure CAS No.
Formula FW (g/mol) Forms
Density (g/ml)
Hydroxylamine-O-sulfonic Acid HOSA 2950-43-8 H3NO
4S
113.09Solid 2.2 g/cc
O-Benzylhydroxylamine HydrochlorideO-Benzyhydroxylammonium Chloride
OBHA•HCl 2687-43-6 C7H
10ClNO
159.62Solid .370 g/cc
O-Methylhydroxylamine HydrochlorideO-Methylhydroxylammonium Chloride
O-MHA•HCl 593-56-6 CH6ClNO
83.5230% Solution 1.15 g/ml
N,O-Dimethylhydroxylamine HydrochlorideN,O-Dimethylhydroxylammonium Chloride
NODMHA•HCl 6638-79-5 C2H
8ClNO
97.54Solid
N-Hydroxyphtalimide NHPI 524-38-9 C8H
5NO
3
163.13Solid
2, 3-Butanedione monoxime BDMO 57-71-6 C4H
7NO
2
101.11Solid
High Purity Iron SaltsBASF reliably helps to fulfill the legal restrictions like the EMEA directive (European Medicine Agency) and recommendations from US Pharmacopoeia (USP) by offering high purity solutions with trace metal impurities in single digit ppm level. BASF’s high purity iron salts are based on BASF’s experienced and well-established iron technology. Full backward integration ensures a reliable supply of raw materials. BASF offers a high variety of different anions and also other high purity metals on request.
Name/SynonymAbbreviation/ Trade Name Structure CAS No.
Formula FW (g/mol) Forms
Density (g/ml)
Ferric Chloride Solution High Purity
Iron(III) Chloride Solution
7705-08-0 FeCl3
162.2012% Solution (Fe3+) 1.36 g/ml
Ferric Sulfate SolutionHigh Purity
Iron(III) Sulfate Solution
10028-20-5 Fe2(SO
4)3
399.8812% Solution (Fe3+) 1.50 g/ml
Ferrous Sulfate SolutionHigh Purity
Iron(II) Sulfate Solution
7720-78-7 FeSO4
151.919% Solution
BASF offers a large variety of different anions (aqueous and organic solutions) and other high purity metal salts on request.
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Symbols2, 3-Butanedione monoxime .....................................................................................62-Hydroxyacetophenone ...........................................................................................52-Picoline borane .....................................................................................................14-Hydroxyacetophenone ...........................................................................................55-Ethyl-2-methylpyridine borane ..............................................................................19-Borabicyclo[3.3.1]nonane ......................................................................................3(-)-Diisopinocampheylchloroborane ..........................................................................2(+)-Diisopinocampheylchloroborane .........................................................................2(R)-Methyl oxazaborolidine ........................................................................................2(S)-Methyl oxazaborolidine ........................................................................................2
BBis(pinacolato)diboron ..............................................................................................1Borane tetrahydrofuran complex ...............................................................................1Butylamine borane ....................................................................................................1
CCatecholborane.........................................................................................................1
DDibutylboron triflate ..................................................................................................3Dimethylamine borane ..............................................................................................1Dimethylsulfide borane .............................................................................................1
FFerric Chloride Solution .............................................................................................6Ferric Sulfate Solution ...............................................................................................6Ferrous Sulfate Solution ............................................................................................6
HHydroxylamine-O-sulfonic Acid .................................................................................6
LLithium Hexamethyldisilazane ...................................................................................5Lithium triethylborohydride .......................................................................................2Lithium tri-sec-butylborohydride ...............................................................................2
MMethoxydiethylborane ...............................................................................................3
NN-Hydroxyphtalimide ................................................................................................6N,N-Diethylaniline borane .........................................................................................1N, O,-Dimethylhydroxylamine Hydrochloride .............................................................6
OO-Benzylhydroxylamine Hydrochloride ......................................................................6O-Methylhydroxylamine Hydrochloride ......................................................................6
PPhenyl Acetate ..........................................................................................................5Pinacolborane ...........................................................................................................1Potassium 3,7-Dimethyl-3-octylate ...........................................................................4Potassium Ethylate ...................................................................................................4Potassium Hexamethyldisilazane ..............................................................................5Potassium Methylate.................................................................................................4Potassium superoxide ...............................................................................................5Potassium tert.-Amylate............................................................................................4Potassium tert.-Butylate ...........................................................................................4Pyridine borane .........................................................................................................1
SSodium Ethylate ........................................................................................................4Sodium Hexamethyldisilazane ...................................................................................5Sodium Mentholate ...................................................................................................4Sodium Methylate .....................................................................................................4Sodium n-Butylate ....................................................................................................4Sodium Potassium Alloy ............................................................................................5Sodium tert.-Amylate ................................................................................................4Sodium tert.-Butylate ................................................................................................4Sodium triacetoxyborohydride ...................................................................................2Sodium tri-sec-butylborohydride ...............................................................................2
TTriethylamine borane ................................................................................................1Triethylborane ...........................................................................................................3Triethylborane-1,3-diaminopropane complex ............................................................3Trimethoxyboroxin ....................................................................................................3Trimethylboroxin .......................................................................................................3Tri-n-butylborane ......................................................................................................3Tri-n-butylborane-3-methoxypropylamine complex ...................................................3
Index
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While the descriptions, designs, data and information contained herein are presented in good faith and believed to be accurate, it is provided for your guidance only. Because many factors may affect processing or application/use, we recommend that you make tests to determine the suitability of a product for your particular purpose prior to use. NO WARRANTIES OF ANY KIND, EITHER EXPRESS OR IMPLIED, INCLUDING WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE, ARE MADE REGARDING PRODUCTS DESCRIBED OR DESIGNS, DATA OR INFORMATION SET FORTH, OR THAT THE PRODUCTS, DESIGNS, DATA OR INFORMATION MAY BE USED WITHOUT INFRINGING THE INTELLECTUAL PROPERTY RIGHTS OF OTHERS. IN NO CASE SHALL THE DESCRIPTIONS, INFORMATION, DATA OR DESIGNS PROVIDED BE CONSIDERED A PART OF OUR TERMS AND CONDITIONS OF SALE.
Rev. 02/2013
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