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

David J Del Valle; Michael J Krische

doi:10.1021/ja4061273

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

J Am Chem Soc. 2013 Jul 31;135(30):10986-9. doi: 10.1021/ja4061273. Epub 2013 Jul 17.

Authors

David J Del Valle¹, Michael J Krische

Affiliation

¹ Department of Chemistry and Biochemistry, University of Texas at Austin, Austin, Texas 78712, USA.

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.

Publication types

Research Support, N.I.H., Extramural
Research Support, Non-U.S. Gov't

MeSH terms

Alanine / analogs & derivatives*
Alanine / chemical synthesis
Alanine / chemistry
Carbon / chemistry*
Chemistry Techniques, Synthetic
Hydrogenation
Lactams, Macrocyclic / chemical synthesis*
Lactams, Macrocyclic / chemistry*

Substances

Lactams, Macrocyclic
Carbon
trienomycin A
Alanine

Abstract

Publication types

MeSH terms

Substances

Grants and funding