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

Total synthesis of pseudomonic acid C

…, HL Lee, T Mitt, G Pizzolato, EG Baggiolini…

Index: Barrish, Joel C.; Lee, Hsi Lin; Mitt, Toomas; Pizzolato, Giacomo; Baggiolini, Enrico G; Uskokovic, Milan R Journal of Organic Chemistry, 1988 , vol. 53, # 18 p. 4282 - 4295

Full Text: HTML

Citation Number: 40

Abstract

Two approaches to the synthesis of aldehyde 28, a key intermediate in the total synthesis of pseudomonic acid C, were developed. One asymmetric route from the chiral hydroxy ester 11 proceeded in 13 steps via the hydroxy lactone 17. A shorter approach involved the Lewis acid catalyzed cycloaddition of formaldehyde to the chiral diene 23a to give 22a, which was separated from its diastereomer and then converted into 28 in seven steps. The ...

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

~91%

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

[S-(R*,R*)]-5,6-dihydro-N-(1-phenylethyl)-2H-pyran-2-acetamide Structure

[S-(R*,R*)]-5,6...

~%

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

(5S-cis)-5,6-dihydro-6-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-ol Structure

(5S-cis)-5,6-di...

~%

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

[S-(R*,R*)]-5,6-dihydro-N-(1-phenylethyl)-2H-pyran-2-acetamide Structure

[S-(R*,R*)]-5,6...

~%

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

~%

1-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)propan-2-ol Structure

1-((3aS,4S,7S,7...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

1-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)propan-2-ol Structure

1-((3aS,4S,7S,7...

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethanol Structure

2-((3aS,4S,7S,7...

~98%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)acetaldehyde Structure

2-((3aS,4S,7S,7...

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)acetaldehyde Structure

2-((3aS,4S,7S,7...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)acetaldehyde Structure

2-((3aS,4S,7S,7...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)acetaldehyde Structure

2-((3aS,4S,7S,7...

[S-(R*,R*)]-5,6-dihydro-N-(1-phenylethyl)-2H-pyran-2-acetamide Structure

[S-(R*,R*)]-5,6...

~74%

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethanol Structure

2-((3aS,4S,7S,7...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethanol Structure

2-((3aS,4S,7S,7...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethanol Structure

2-((3aS,4S,7S,7...

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

~%

2-((3aS,4S,7S,7aR)-7-((4R,5S,E)-5-((tert-butyldimethylsilyl)oxy)-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethanol Structure

2-((3aS,4S,7S,7...

(2R,3R,E)-2-((tert-butyldimethylsilyl)oxy)-6-((3aS,4S,7S,7aR)-4-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl)-3-methylhex-4-en-1-ol Structure

(2R,3R,E)-2-((t...

~63%

tert-butyl(2-((3aS,4S,7S,7aR)-7-((4R,5R,E)-5-((tert-butyldimethylsilyl)oxy)-6-iodo-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethoxy)diphenylsilane Structure

tert-butyl(2-((...

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

~%

tert-butyl(2-((3aS,4S,7S,7aR)-7-((4R,5R,E)-5-((tert-butyldimethylsilyl)oxy)-6-iodo-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethoxy)diphenylsilane Structure

tert-butyl(2-((...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

tert-butyl(2-((3aS,4S,7S,7aR)-7-((4R,5R,E)-5-((tert-butyldimethylsilyl)oxy)-6-iodo-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethoxy)diphenylsilane Structure

tert-butyl(2-((...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

tert-butyl(2-((3aS,4S,7S,7aR)-7-((4R,5R,E)-5-((tert-butyldimethylsilyl)oxy)-6-iodo-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethoxy)diphenylsilane Structure

tert-butyl(2-((...

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

~%

tert-butyl(2-((3aS,4S,7S,7aR)-7-((4R,5R,E)-5-((tert-butyldimethylsilyl)oxy)-6-iodo-4-methylhex-2-en-1-yl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-4-yl)ethoxy)diphenylsilane Structure

tert-butyl(2-((...

(3aS,7R,7aR)-7-iodohexahydro-2H-furo[3,2-b]pyran-2-one Structure

(3aS,7R,7aR)-7-...

~%

(2R,3R,E)-2-((tert-butyldimethylsilyl)oxy)-6-((3aS,4S,7S,7aR)-4-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl)-3-methylhex-4-en-1-ol Structure

(2R,3R,E)-2-((t...

(R,E)-N-(1-phenylethyl)hexa-3,5-dienamide Structure

(R,E)-N-(1-phen...

~%

(2R,3R,E)-2-((tert-butyldimethylsilyl)oxy)-6-((3aS,4S,7S,7aR)-4-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl)-3-methylhex-4-en-1-ol Structure

(2R,3R,E)-2-((t...

(2S-cis)-5,6-dihydro-N,N-dimethyl-2-[2-[[(1,1-dimethylethyl)diphenylsilyl]oxy]ethyl]-2H-pyran-5-acetamide Structure

(2S-cis)-5,6-di...

~%

(2R,3R,E)-2-((tert-butyldimethylsilyl)oxy)-6-((3aS,4S,7S,7aR)-4-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl)-3-methylhex-4-en-1-ol Structure

(2R,3R,E)-2-((t...

2-((3S,4R,5R,6S)-6-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-4,5-dihydroxytetrahydro-2H-pyran-3-yl)-N,N-dimethylacetamide Structure

2-((3S,4R,5R,6S...

~%

(2R,3R,E)-2-((tert-butyldimethylsilyl)oxy)-6-((3aS,4S,7S,7aR)-4-(2-((tert-butyldiphenylsilyl)oxy)ethyl)-2,2-dimethyltetrahydro-3aH-[1,3]dioxolo[4,5-c]pyran-7-yl)-3-methylhex-4-en-1-ol Structure

(2R,3R,E)-2-((t...

(S)-3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methyl-1-butanol 4-methylbenzenesulfonate Structure

(S)-3-[[(1,1-di...

~%

(2S,3S)-3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methyl-1-(phenylsulfonyl)butane Structure

(2S,3S)-3-[[(1,...

(S)-3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]-2-methyl-1-butanol 4-methylbenzenesulfonate Structure

(S)-3-[[(1,1-di...

~91%

tert-butyl(((2S,3S)-4-iodo-3-methylbutan-2-yl)oxy)dimethylsilane Structure

tert-butyl(((2S...