Review: Angew. Chem. Int. Ed. 2000

Philipp Gritsch

Review:Angew. Chem. Int. Ed. 2000

Kalesse & Gaich Seminar

Group seminar Kalesse & Gaich

2. 11. 2011

Angew. Chem. Int. Ed. 20002. 11. 2011 Philipp Gritsch

Publication Record

- 4617 pages

- 1086 papers in total

- 33 „Total Synthesis“ as research topic

Notable events

- Wladimir Putin is elected President of Russia

- First year of the FPÖ-ÖVP Government in Austria

- American Beauty wins Academy Award for Best Picture

- Maschen-Draht-Zaun by Stefan Raab is No. 1 for 14 weeks

- First permanent resident aboard the ISS

- EXPO 2000 in Hannover

2Kalesse & Gaich Seminar

Most cited papers

1) (2729) Ionic Liquids – new „Solution“ for Transition Metal Catalysis;

Wasserscheid, P.; Keim, W. Angew. Chem. Int. Ed. 2000, 39(21), 3772 – 3789;

2) (1488) Olefin Metathesis and Beyond;

Fürstner, A. Angew. Chem. Int. Ed. 2000, 39(17), 3012 – 3043;

3) (1363) Multicomponent Reactions with Isocyanides;

Domling, A.; Ugi, I. Angew. Chem. Int. Ed. 2000, 39(18), 3168 – 3210;


Detailed Syntheses Concise Syntheses

NH2N

OMe

HO

HH

Me

O O

O O

OO

n-Pr

H

HMeO2C

HOOAc

H

OH

O

OH

H

O

OH

O

Bryostatin 3


OP

O

OH

OH

Cl

FR901483

NH

O

N

NH

O

O

MeO

( )-Spirotyprostatin B


Asymmetric, Stereocontrolled Total Synthesis of Paraherquamide A; Williams, R. M.; Cao, J.;Tsujishima, H. Angew. Chem. Int. Ed. 2000, 39(14), 2540 - 2544

N

Boc

CO2Et

O

(a) Baker's Yeast

60-80%90% ee

N

Boc

CO2Et

OH

N

Boc

CO2Et

OH

I

OTBS

(b) LDA, THF, HMPA

OTBS

(c) 5.7 equiv MOMCl, (i-Pr)2NEt, CHCl2(d) 2.7 equiv ZnBr2, CH2Cl2(e) K2CO3, 2.0 equiv BrCH2COBr, CH2Cl2

N CO2Et

OBr

58%86%

(3 steps)

(f) NH3 in MeOH(g) 3.0 equiv NaH, PhMe N

ONH

O79 %

(2 steps)

(h) 1.3 equiv n-BuLi, THF, 1.1 equiv ClCO2Me, -78 °C;then 5 equiv LiHMDS, 4.0 equiv ClCO2Me, -78 °C N

OMOM OTBS

ONCO2Me

O

CO2Me

93%


OMOM OTBS OMOM OTBS(2 steps) OMOM OTBS

N

O

OOTBS

(i) 0.7 equiv n-Bu3P

NH

N

O

OMOMO

TBSO

CO2Me

H

NH

Me2N

O

O

OTBS

70%3:1

(j) 5.0 equiv LiCl, H2O, HMPA, 105 °C, 5 h

89%

N

O

OOTBS

NH

N

O

OMOMO

TBSO

H

H

syn 52%anti 78%


(k) 2.5 equiv Me3OBF4, CH2Cl2, Cs2CO3, 25 °C(l) 3.0 equiv Boc2O, DMAP, CH2Cl2, 0 °C(m) 3.3 equiv TBAF, THF, 25 °C

N

O

OOH

N

N

O

OMeMOMO

HO

H

Boc

N

O

OOTBS

N

N

O

OMeMOMO

Cl

H

Boc

(n) 1.1 equiv MsCl, collidine, CH2Cl2, 0 °C(o) 2.0 equiv TBSOTf, 2.6-lutidine, CH2Cl2, 0 °C

68-71%

(p) 20 equiv NaH, THF, reflux, 30 h

87%

N

O

N

OMOM

H

H

OMe

Boc

OTBS

(q) 3.1 equiv AgBF4, 4.68 equiv PdCl2, MeCN,then NaBH4, EtOH

O


exclusive synO

N

N

H

N O

O

N

N

OMOM

H

H

OMe

Boc

OTBS

(r) 0.1M HCl, THF(s) 2-hydroxypyridine, PhMe, 120 °C, 2 h63 % (3 steps)

(t) 5.0 equiv DIBAL-H, CH2Cl2, 0 °C50-70%

N O

O

N

N

OMOM

H

H

O

Boc

OTBS

H

O

O

(u) NaH, MeI, DMF, 0 °C, 96%(v) 6 equiv Bromocatechole borane,

CH2Cl2, 0 °C, 91%

(w) 5.0 equiv DMP, 85%(x)TFA, CH2Cl2, 97%

HN O

O

N

N

OH

O

OH

Me

(y) 1.5 equiv t-BuOCl, pyridinethen 5.0 equiv p-TsOH THF, H2O, refl.

(z) 5.0 equiv (PhO)3PMeI, DMPU(aa) MeMgBr, THF

Paraherquamide A

NH

O

O

O

N

N

OMe

OH

Me

H


A Concise Stereoselective Route to the Pentacyclic Framework in Arisugacin A and Territrem B;Hsung, R. P.; Zehnder, L. R.; Wang, J.; Golding, G. M. Angew. Chem. Int. Ed. 2000, 39(21), 3876 - 3879

O5 steps

overall 46%

O

O

(±)

(a) n-decane, refl., 23 h

61%

OO

(b) m-CBPA, CH2Cl2, 0°C, 24hpH buffer 7

59%

OO

O

3:1 to 6:1

(c) LiAlH4, Et2O,-78 °C to r t 2 h

OHOH

(d) Ac2O, Pyr, r.t., 24 h(e) DMP CH2Cl2 r t 2 h

OOAc

(f) K2CO3, MeOH,r t 24h

OHO (g) PCC, CH2Cl2r t 40 h

Nicolaou, K.C.; Li, W.S. J. Chem. Soc. Chem. Commun. 1985, 421


78 C to r.t., 2 h

O

(e) DMP, CH2Cl2, r.t., 2 h

90%

O

r.t., 24h

95%

r.t., 40 h

O

O

O

(h) Piperidinium AcetateNa2SO4, EtOAc, 80 °C, 1 h

O

O

NR2

O

R

OMe

OMe

OH

(i) EtOAc, 80 °C, 20 h

O

O

O

OO

O

OMe

OMe

R

68 - 71%

Arisugacin A R = HTerritrem B R = OMe


An Enantiospecific Synthesis of the Potent Immunosuppressant FR901483;Sorensen, E. J.; Scheffler, G.; Seike, H. Angew. Chem. Int. Ed. 2000, 39(24), 4593 - 4596



A New Enantioselective Approach to Total Synthesis of the Securinega Alkaloids: Application to (-)-Norsecurinine and Phyllantine;

Weinreb, S.M.; Han, G.; LaPorte, M. G.; Folmer, J. J.; Werner, K. M.; Angew. Chem. Int. Ed. 2000, 39(1), 237 - 240



HO OR

R = H

R = TBS(a) TBSCl, imidazole,

CH2Cl2, r.t., 1 h, 55%

(b) TBHP, Ti(Oi-Pr)4, D-(-)DET,MS 4 Å, CH2Cl2, -20 °C, 2 h, 83%

HO OTBSO

(c) Ti(Oi-Pr)4, PivOH,PhH, 0 °C, 2 h, 83%

HO OTBSOPiv

HO

OROPiv

O

O

(d) 2,2-dimethoxypropane,CSA, CH2Cl2, 0 °C, 2 h, 88%

R = TBS

R = H(e) BuN4F, THF, r.t.

3 h, 99%

(f) TBHP, Ti(Oi-Pr)4, L-(+)DET,MS 4 Å, CH2Cl2, -20 °C, 3 h, 89%

OHOPIv

O

O O

(h) A OH/H O 4 1 t 5 h

PhS

Li

Total Synthesis of (+)-Eurylene and (+)-14-Deacetyleurylene;Morimoto, Y.; Muragaki, K.; Iwai, T.; Morishita, Y.; Kinoshita, T. Angew. Chem. Int. Ed. 2000, 39(22), 4082 - 4084


(g) Ti(OMPM)4, MPMOH,PhH, 60 °C, 12 h

OHOPIv

O

O

MPMO

OH(h) AcOH/H2O 4:1, r.t., 5 h(i) MsCl, pyr, CH2Cl2, 0 °C to r.t., 5 h(j) K2CO3, MeOH, r.t., 1 h

OPIvMPMO

O O

(k) TMEDA, THF, - 78 °C, 30 minthen 0 °C, 2 h

41 % (4 steps)

OHMPMO

HO OH

PhS SPh(l) Na, THF/i-PrOH 2:1 refl, 15 h, 86%(m) Ac2O pyr, r.t., 12 h, 91 %(n) DDQ, MS 4 Å, CH2Cl2, 0 °C, 2 h, 68%

OAcHO

HO OH

(o) [(CF3CO2)ReO3.2CH3CN], TFAA, 'CH2Cl2/MeCN 9:1, -40 °C, 1.5 h, 84%

OAcHO

OHOHHO

(p) PCC, CH2Cl2, r.t. 30 min, 47%

HOO

HOAcO OH H OH

(+)-14-deacetyl eurylene


Total Synthesis of (—)-Spirotryprostatin B and Three Stereoisomers;Overman, L. E.; Rosen, D. M. Angew. Chem. Int. Ed. 2000, 39(24), 4596 - 4599

NSEM

O

N

NH

O

O

MeOON

SEMI

NH

N

O

OH

NSEM

O

NH

NH

O

O

MeOPdL2I

[Pd2(dba)3].CHCl3(otol)3P, KOAc

THF, 70 °C72% 1:1


NSEM

O

N

NH

O

O

MeO

Me2AlCl, i-Pr2NEt

NH

O

N

NH

O

O

MeO

( )-Spirotyprostatin B 1 : 1


PMBO

O O

PhSe

(a) NaIO4, NaHCO3, MeOH/H2O, 20 °C, 2 h(b) DBU, CH2=C(OMe)OTBS, Xylenes, refl., 6 h

O

O

Me

PMBO Me

Me

Total Synthesis of the Antimicrotubule Agent (+)-Discodermolide Using Boron-Mediated Aldol Reactions;Paterson, I.; Florence, G. J.; Gerlach, K.; Scott, J. P. Angew. Chem. Int. Ed. 2000, 39(2), 377- 380


OO

OH

HO

OH

OH O

NH2

O

(+) Discodermolide

OO

Me

PMBO Me

Me

O

O

Me

PMBO


A Stereoselective Total Synthesis of Zaragozic Acid A based on an Acetal [1,2] Wittig Rearrangement;Tomooka, K.; Kikuchi, M.; Igawa, K.; Suzuki, M.; Keong, P.-H.; Nakai, T. Angew. Chem. Int. Ed. 2000, 39(24), 4502 - 4505



Asymmetric Synthesis of Phorboxazole B – Part I: Synthesis of the C20-C38 and C39-C46 Subunits;Evans, D. A.; Cee, V. J.; Smith, T. E.; Fitch, D. M., Cho, P. S. Angew. Chem. Int. Ed. 2000, 39(14), 2533 - 2536


ON

O

HO

O

OO

O

N

OO

OH

MeO

Br

HOMeO

Phorboxazole B

Entry Phosphonate Yield Z : E

1 94 1.6 : 1


Total Synthesis of Bryostatin 3;Nishiyama, S.; Yamamura, S.; Ohmori, K.; Ogawa, Y.; Obitsu, T.; Ishikawa, Y. Angew. Chem. Int. Ed. 2000, 39(13), 2290 - 2294

H

MeO C

HOOAc

2 90 2.0 : 1

3 92 4.0 : 1

4 85 2.3 : 1


O O

O O

OO

n-Pr

HMeO2C

H

OH

O

OH

H

O

OH

O

Bryostatin 3


Highly diastereoselective Synthesis of Monocyclic and Bicyclic Secondary Diorganozinc Reagents with defined Configuration;Knochel, P.; Boudier, E.; Hupe, E. Angew. Chem. Int. Ed. 2000, 39(13), 2294 - 2997



Entry R a Yield [%] ee [%] b

1 96 81

2 83 93

A Chiral, Nonracemic Enolate with Dynamic Axial Chirality: Direct Asymmetric α-Methylation of α-Amino Acid Derivatives;Kawabata, T.; Suzuki, H.; Nagae, Y.; Fuji, K. Angew. Chem. Int. Ed. 2000, 39(12), 2155 - 2157


3 94 79

4 95 80

5 88 76

6 81 87

7 78 78

aee value for each substrate was >99 %; b determined by HPLC using columns with chiral stationary phase


Entry R1 R2 Yield [%]a

1 Me t-C H 97 (100)

The catalytic Alkylation of Aromatic Imines by Wilkinson's Complex: The Domino Reaction of Hydroacylation and ortho-Alkylation

Jun, C-H.; Hong, J-B.; Kim, Y-H.; Chung, K-Y. Angew. Chem. Int. Ed. 2000, 39(19), 3440 - 3442


1 Me t-C4H9 97 (100)

2 Me C6F5 91 (100)

3 Me Cy 65 (68)

4 Me n-C4H9 94 (97)b

7 Me TMS 92 (96)

9 Me 42 (47)c

10 Me 35

11 Et TMS 93 (100)d

12 n-C5H11 TMS 73(80)e

a GC yields are given in parentheses; b 5.0 equiv of olefin were used; c 3.0 equiv of olefin were

used; d 12% of di-ortho alkylation included; e 16% of di-ortho alkylation included


Entry Alcohol Anhydride / equiv Mol% cat. Time [h] Yield [%]

1 Ac2O / 10 3.0 1 96a

2 Ac2O / 10 0.5 7 95b

Highly Efficient and Versatile Acylation of Alcohols and Bi(OTf)3Otera, J.; Orita, A.; Tanahashi, C.; Kakuda, A. Angew. Chem. Int. Ed. 2000, 39(16), 2877 - 2879


3(PhCO) 2O / 0.5

(t-BuCO)2O / 3.0

3.0

3.0

8

4

2c

99

4 (PhCO) 2O / 5.0 3.0 48 0c

5 (PhCO) 2O / 1.5 3.0 24 90c

6 1-adamatol (t-BuCO)2O / 1.5 3.0 4 94

7 (t-BuCO)2O / 1.5 3.0 4 97

a MeCN used as solvent; b THF used as solvent; c determined by GC


Entry R Rh : Ligand Mol% Rh Conversion [%] ee [%]

1 Me 1 : 1 0.1 100 89.2

2 i-Pr 1 : 1 0.1 100 97.6

3 Ph 1 : 1 0.1 100 96.6

4 o-Br-Ph 1 : 1 0.1 100 89.8

Highly enantioselective Rh-Catalyzed Hydrogenation Reactions based on Chiral Monophosphite LigandsReetz, M.T.; Mehler, G. Angew. Chem. Int. Ed. 2000, 39(21), 3889 - 3890


5 2,6-(Me)2-Ph 1 : 1 0.1 78 39.2

6 2,6-(Ph)2-Ph 1 : 1 0.1 8 28.6

7 (R)-2-(1-phenylethyl) 1 : 1 0.1 100 99.2

8 (S)-2-(1-phenylethyl) 1 : 1 0.1 100 98.2

9 (R)-2-(1-phenylethyl) 1 : 1 0.04 100 99.4

10 (R)-2-(1-phenylethyl) 1 : 1 0.02 100 99.4

11 (R)-2-(1-phenylethyl) 1 : 1 0.01 49 96.2

12 (R)-2-(1-phenylethyl) 1 : 2 0.1 100 99.6

13 (R)-2-(1-phenylethyl) 1 : 4 0.1 100 99.5

14 (R/S)-2-(1-phenylethyl) 1 : 1 0.1 100 98.8

Ph

Me

Ph

Me

(S)-2-(1-phenylethyl)

(R)-2-(1-phenylethyl)


Syntheses not covered

O

O

H

H

S

NH

OOH

OOH

Epithilone B

Shibasaki, M.; Sawada, D.;Angew. Chem. Int. Ed. 2000, 39(1), 209 - 213

O

HO

O

OH

OHO O

(+)-Ratjadone

Kalesse, M.; Christmann, M.; Bhatt, U.; Quitschalle, E. C.;Angew. Chem. Int. Ed. 2000, 39(23), 4364 - 4366


Frondosin B

Danishefsky, S. J.; Inoue, M.; Frontier, A. J.Angew. Chem. Int. Ed. 2000, 39(4), 761 - 764

Review: Angew. Chem. Int. Ed. 2000

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