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Total synthesis of (+)-trienomycins A and F via C-C bond-forming hydrogenation and transfer hydrogenation.

ABSTRACT: The triene-containing C17-benzene ansamycins trienomycins A and F were prepared in 16 steps (longest linear sequence, LLS) and 28 total steps. The C11-C13 stereotriad was generated via enantioselective Ru-catalyzed alcohol CH syn crotylation followed by chelation-controlled carbonyl dienylation. Enantioselective Rh-catalyzed acetylene-aldehyde reductive coupling mediated by gaseous H2 was used to form a diene that ultimately was subjected to diene-diene ring closing metathesis to form the macrocycle. The present approach is 14 steps shorter (LLS) than the prior syntheses of trienomycins A and F, and 8 steps shorter than any prior synthesis of a triene-containing C17-benzene ansamycin.

SUBMITTER: Del Valle DJ

PROVIDER: S-EPMC3757526 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

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Total synthesis of (+)-trienomycins A and F via C-C bond-forming hydrogenation and transfer hydrogenation.

Del Valle David J DJ Krische Michael J MJ

Journal of the American Chemical Society 20130717 30

The triene-containing C17-benzene ansamycins trienomycins A and F were prepared in 16 steps (longest linear sequence, LLS) and 28 total steps. The C11-C13 stereotriad was generated via enantioselective Ru-catalyzed alcohol CH syn crotylation followed by chelation-controlled carbonyl dienylation. Enantioselective Rh-catalyzed acetylene-aldehyde reductive coupling mediated by gaseous H2 was used to form a diene that ultimately was subjected to diene-diene ring closing metathesis to form the macroc ...[more]

PMID: 23862627

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