e.g. Filippa Pettersson or Cancer Res. 75(6) , 1102-12, (2015) or 10.1002/anie.201600521

Total syntheses of epothilones A and B via a macrolactonization-based strategy

…, S Ninkovic, F Sarabia, D Vourloumis…

Index: Nicolaou; Ninkovic; Sarabia; Vourloumis; He; Vallberg; Finlay; Yang Journal of the American Chemical Society, 1997 , vol. 119, # 34 p. 7974 - 7991

Full Text: HTML

Citation Number: 267

Abstract

The total syntheses of epothilones A (1) and B (2) and several analogues thereof are described. The reported strategy relies on a macrolactonization approach and features selective epoxidation of the macrocycle double bond in precursors 3 and 4 (Scheme 1), respectively, as well as high convergency and flexibility. Building blocks 9-12 and 15 were constructed by asymmetric processes and coupled via Wittig, aldol, and ...

(2E)-2-Methyl-3-(2-methyl-1,3-thiazol-4-yl)acrylaldehyde Structure

(2E)-2-Methyl-3...

~72%

(3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-ol Structure

(3S)-2-methyl-1...

(2S,6Z,9S,10E)-9-((tert-butyldimethylsilyl)oxy)-2,10-dimethyl-11-(2-methylthiazol-4-yl)undeca-6,10-dien-1-ol Structure

(2S,6Z,9S,10E)-...

~%

EPOTHILONE C Structure

(2R,3S,10S,7Z,11E)-(tert-butyldimethylsilyloxy)-3,11-dimethyl-12-(2-methyl-1,3-thiazol-4-yl)dodeca-7,11-diene-1,2-diol Structure

(2R,3S,10S,7Z,1...

~%

EPOTHILONE C Structure

2,2-dimethyl-3-oxopentanal Structure

2,2-dimethyl-3-...

~%

EPOTHILONE C Structure

N/A Structure

~%

EPOTHILONE C Structure

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

EPOTHILONE C Structure

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

EPOTHILONE C Structure

N/A Structure

~%

(5S)-6-[tert-butyl(dimethyl)silyl]oxy-5-methylhexanal Structure

(5S)-6-[tert-bu...

N/A Structure

~%

(5S)-6-[tert-butyl(dimethyl)silyl]oxy-5-methylhexanal Structure

(5S)-6-[tert-bu...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(4S,6E)-4-(tert-butyldimethylsilanyloxy)-5-methyl-6-(2-methyl-1,3-thiazol-4-yl)-5-hexene-1,2-diol Structure

(4S,6E)-4-(tert...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-{[(tert-butyl)dimethylsilyl]oxy}-7-hydroxy-4,4-dimethylheptan-3-one Structure

(5S)-5-{[(tert-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

1-{1-[(1E)-1-methyl-2-(2-methyl(1,3-thiazol-4-yl))vinyl](1S)(3Z)-4-methylhepta-3,6-dienyloxy}-1,1,2,2-tetramethyl-1-silapropane Structure

1-{1-[(1E)-1-me...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(S,4Z,8E)-7-((tert-butyldimethylsilyl)oxy)-4,8-dimethyl-9-(2-methylthiazol-4-yl)nona-4,8-dien-1-ol Structure

(S,4Z,8E)-7-((t...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-((S,1E,5Z)-3-((tert-butyldimethylsilyl)oxy)-9-iodo-2,6-dimethylnona-1,5-dien-1-yl)-2-methylthiazole Structure

4-((S,1E,5Z)-3-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2E,6E)(5S)-6-methyl-7-(2-methyl-(1,3-thiazol-4-yl))-2-prop-2-enyl-5-(1,1,2,2-tetramethyl-1-silapropoxy)hepta-2,6-dien-1-ol Structure

(2E,6E)(5S)-6-m...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

methyl (S,2E,6E)-2-allyl-5-((tert-butyldimethylsilyl)oxy)-6-methyl-7-(2-methylthiazol-4-yl)hepta-2,6-dienoate Structure

methyl (S,2E,6E...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2S,6Z,9S,10E)-9-((tert-butyldimethylsilyl)oxy)-N-((S)-2-(methoxymethyl)pyrrolidin-1-yl)-2,6,10-trimethyl-11-(2-methylthiazol-4-yl)undeca-6,10-dien-1-imine Structure

(2S,6Z,9S,10E)-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S,6R,7S,8S,12Z,15S,16E)-3,7,15-tris((tert-butyldimethylsilyl)oxy)-4,4,6,8,12,16-hexamethyl-17-(2-methylthiazol-4-yl)-5-oxoheptadeca-12,16-dienal Structure

(3S,6R,7S,8S,12...

~89%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

Ethyl 2-methylthiazole-4-carboxylate Structure

Ethyl 2-methylt...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

tert-Butyldimethylsilyl Trifluoromethanesulfonate Structure

tert-Butyldimet...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

4-Formyl-2-methylthiazole Structure

4-Formyl-2-meth...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

2,2-dimethyl-3-oxopentanal Structure

2,2-dimethyl-3-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(4S,6E)-4-(tert-butyldimethylsilanyloxy)-5-methyl-6-(2-methyl-1,3-thiazol-4-yl)-5-hexene-1,2-diol Structure

(4S,6E)-4-(tert...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(5S)-5-{[(tert-butyl)dimethylsilyl]oxy}-7-hydroxy-4,4-dimethylheptan-3-one Structure

(5S)-5-{[(tert-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

1-{1-[(1E)-1-methyl-2-(2-methyl(1,3-thiazol-4-yl))vinyl](1S)(3Z)-4-methylhepta-3,6-dienyloxy}-1,1,2,2-tetramethyl-1-silapropane Structure

1-{1-[(1E)-1-me...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(S,4Z,8E)-7-((tert-butyldimethylsilyl)oxy)-4,8-dimethyl-9-(2-methylthiazol-4-yl)nona-4,8-dien-1-ol Structure

(S,4Z,8E)-7-((t...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

4-((S,1E,5Z)-3-((tert-butyldimethylsilyl)oxy)-9-iodo-2,6-dimethylnona-1,5-dien-1-yl)-2-methylthiazole Structure

4-((S,1E,5Z)-3-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(2E,6E)(5S)-6-methyl-7-(2-methyl-(1,3-thiazol-4-yl))-2-prop-2-enyl-5-(1,1,2,2-tetramethyl-1-silapropoxy)hepta-2,6-dien-1-ol Structure

(2E,6E)(5S)-6-m...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

methyl (S,2E,6E)-2-allyl-5-((tert-butyldimethylsilyl)oxy)-6-methyl-7-(2-methylthiazol-4-yl)hepta-2,6-dienoate Structure

methyl (S,2E,6E...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

(2S,6Z,9S,10E)-9-((tert-butyldimethylsilyl)oxy)-N-((S)-2-(methoxymethyl)pyrrolidin-1-yl)-2,6,10-trimethyl-11-(2-methylthiazol-4-yl)undeca-6,10-dien-1-imine Structure

(2S,6Z,9S,10E)-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)-5-oxoheptadeca-12,16-dienoic acid Structure

(3S,7S,8S,12Z,1...

tert-Butyldimethylsilyl Trifluoromethanesulfonate Structure

tert-Butyldimet...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-Formyl-2-methylthiazole Structure

4-Formyl-2-meth...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

2,2-dimethyl-3-oxopentanal Structure

2,2-dimethyl-3-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(4S,6E)-4-(tert-butyldimethylsilanyloxy)-5-methyl-6-(2-methyl-1,3-thiazol-4-yl)-5-hexene-1,2-diol Structure

(4S,6E)-4-(tert...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-{[(tert-butyl)dimethylsilyl]oxy}-7-hydroxy-4,4-dimethylheptan-3-one Structure

(5S)-5-{[(tert-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

1-{1-[(1E)-1-methyl-2-(2-methyl(1,3-thiazol-4-yl))vinyl](1S)(3Z)-4-methylhepta-3,6-dienyloxy}-1,1,2,2-tetramethyl-1-silapropane Structure

1-{1-[(1E)-1-me...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(S,4Z,8E)-7-((tert-butyldimethylsilyl)oxy)-4,8-dimethyl-9-(2-methylthiazol-4-yl)nona-4,8-dien-1-ol Structure

(S,4Z,8E)-7-((t...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-((S,1E,5Z)-3-((tert-butyldimethylsilyl)oxy)-9-iodo-2,6-dimethylnona-1,5-dien-1-yl)-2-methylthiazole Structure

4-((S,1E,5Z)-3-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2E,6E)(5S)-6-methyl-7-(2-methyl-(1,3-thiazol-4-yl))-2-prop-2-enyl-5-(1,1,2,2-tetramethyl-1-silapropoxy)hepta-2,6-dien-1-ol Structure

(2E,6E)(5S)-6-m...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

methyl (S,2E,6E)-2-allyl-5-((tert-butyldimethylsilyl)oxy)-6-methyl-7-(2-methylthiazol-4-yl)hepta-2,6-dienoate Structure

methyl (S,2E,6E...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2S,6Z,9S,10E)-9-((tert-butyldimethylsilyl)oxy)-N-((S)-2-(methoxymethyl)pyrrolidin-1-yl)-2,6,10-trimethyl-11-(2-methylthiazol-4-yl)undeca-6,10-dien-1-imine Structure

(2S,6Z,9S,10E)-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

Ethyl 2-methylthiazole-4-carboxylate Structure

Ethyl 2-methylt...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,15-tris[[tert-butyl(dimethyl)silyl]oxy]-7-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(2S)-2-methyl-6-phenylmethoxyhexan-1-ol Structure

(2S)-2-methyl-6...

1-{1-[(1E)-1-methyl-2-(2-methyl(1,3-thiazol-4-yl))vinyl](1S)(3Z)-4-methylhepta-3,6-dienyloxy}-1,1,2,2-tetramethyl-1-silapropane Structure

1-{1-[(1E)-1-me...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(S,4Z,8E)-7-((tert-butyldimethylsilyl)oxy)-4,8-dimethyl-9-(2-methylthiazol-4-yl)nona-4,8-dien-1-ol Structure

(S,4Z,8E)-7-((t...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-((S,1E,5Z)-3-((tert-butyldimethylsilyl)oxy)-9-iodo-2,6-dimethylnona-1,5-dien-1-yl)-2-methylthiazole Structure

4-((S,1E,5Z)-3-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2E,6E)(5S)-6-methyl-7-(2-methyl-(1,3-thiazol-4-yl))-2-prop-2-enyl-5-(1,1,2,2-tetramethyl-1-silapropoxy)hepta-2,6-dien-1-ol Structure

(2E,6E)(5S)-6-m...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

methyl (S,2E,6E)-2-allyl-5-((tert-butyldimethylsilyl)oxy)-6-methyl-7-(2-methylthiazol-4-yl)hepta-2,6-dienoate Structure

methyl (S,2E,6E...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2S,6Z,9S,10E)-9-((tert-butyldimethylsilyl)oxy)-N-((S)-2-(methoxymethyl)pyrrolidin-1-yl)-2,6,10-trimethyl-11-(2-methylthiazol-4-yl)undeca-6,10-dien-1-imine Structure

(2S,6Z,9S,10E)-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(5S)-5,7-Bis-{[tert-butyldimethylsilyl)oxy]}-4,4-dimethylheptan-3-one Structure

(5S)-5,7-Bis-{[...

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

(5S)-5,7-Bis-{[tert-butyldimethylsilyl)oxy]}-4,4-dimethylheptan-3-one Structure

(5S)-5,7-Bis-{[...

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

(5S)-5,7-Bis-{[tert-butyldimethylsilyl)oxy]}-4,4-dimethylheptan-3-one Structure

(5S)-5,7-Bis-{[...

Ethyl 2-methylthiazole-4-carboxylate Structure

Ethyl 2-methylt...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

tert-Butyldimethylsilyl Trifluoromethanesulfonate Structure

tert-Butyldimet...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-Formyl-2-methylthiazole Structure

4-Formyl-2-meth...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

2,2-dimethyl-3-oxopentanal Structure

2,2-dimethyl-3-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyloct-7en-3-one Structure

(5S)-5-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S)-3-(tert-butyl-dimethyl-silanyloxy)-4,4-dimethyl-5-oxo-heptanal Structure

(3S)-3-(tert-bu...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(4S,6E)-4-(tert-butyldimethylsilanyloxy)-5-methyl-6-(2-methyl-1,3-thiazol-4-yl)-5-hexene-1,2-diol Structure

(4S,6E)-4-(tert...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(5S)-5-{[(tert-butyl)dimethylsilyl]oxy}-7-hydroxy-4,4-dimethylheptan-3-one Structure

(5S)-5-{[(tert-...

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-1,3,7,15-tetrakis[[tert-butyl(dimethyl)silyl]oxy]-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S,4E)-3-{[tert-butyl(dimethyl)silyl]oxy}-4-methyl-5-(2-methyl-1,3-thiazol-4-yl)pent-4-en-1-al Structure

(3S,4E)-3-{[ter...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(2E)-2-Methyl-3-(2-methyl-1,3-thiazol-4-yl)acrylaldehyde Structure

(2E)-2-Methyl-3...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

(3S)-2-methyl-1-(2-methyl-1,3-thiazol-4-yl)hexa-1,5-dien-3-ol Structure

(3S)-2-methyl-1...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

N/A Structure

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

Ethyl 2-methylthiazole-4-carboxylate Structure

Ethyl 2-methylt...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

tert-Butyldimethylsilyl Trifluoromethanesulfonate Structure

tert-Butyldimet...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

4-Formyl-2-methylthiazole Structure

4-Formyl-2-meth...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

2,2-dimethyl-3-oxopentanal Structure

2,2-dimethyl-3-...

~%

(3S,7S,8S,12Z,15S,16E)-3,7,15-tris[[tert-butyl(dimethyl)silyl]oxy]-1-hydroxy-4,4,6,8,12,16-hexamethyl-17-(2-methyl-1,3-thiazol-4-yl)heptadeca-12,16-dien-5-one Structure

(3S,7S,8S,12Z,1...

EPOTHILONE C Structure

~66%

Epothilone A Structure

An Efficient Total Synthesis of (−)-Epothilone B

[Wang, Jie; Sun, Bing-Feng; Cui, Kai; Lin, Guo-Qiang Organic Letters, 2012 , vol. 14, # 24 p. 6354 - 6357]

Total synthesis of epothilones B and D: Stannane equivalents...

[Keck, Gary E.; Giles, Robert L.; Cee, Victor J.; Wager, Carrie A.; Yu, Tao; Kraft, Matthew B. Journal of Organic Chemistry, 2008 , vol. 73, # 24 p. 9675 - 9691]

Total Synthesis of (−)??Epothilone A

[Schinzer, Dieter; Bauer, Armin; Boehm, Oliver M.; Limberg, Anja; Cordes, Martin Chemistry - A European Journal, 1999 , vol. 5, # 9 p. 2483 - 2491]

Total synthesis of 12, 13-desoxyepothilone B (Epothilone D)

[Broadrup, Robert L.; Sundar, Hema M.; Swindell, Charles S. Bioorganic Chemistry, 2005 , vol. 33, # 2 p. 116 - 133]

Total syntheses of epothilones A and B

[Dongfang, Meng; Bertinato, Peter; Balog, Aaron; Su, Dai-Shi; Kamenecka, Ted; et al. Journal of the American Chemical Society, 1997 , vol. 119, # 42 p. 10073 - 10092]