Asymmetric total synthesis of (+)-aphanamol I based on the transition metal catalyzed [5 + 2] cycloaddition of allenes and vinylcyclopropanes

P A Wender; L Zhang

doi:10.1021/ol006085q

Asymmetric total synthesis of (+)-aphanamol I based on the transition metal catalyzed [5 + 2] cycloaddition of allenes and vinylcyclopropanes

Org Lett. 2000 Jul 27;2(15):2323-6. doi: 10.1021/ol006085q.

Authors

P A Wender¹, L Zhang

Affiliation

¹ Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA. [email protected]

PMID: 10930274
DOI: 10.1021/ol006085q

Abstract

A concise asymmetric total synthesis of (+)-aphanamol I is described, based on the transition metal catalyzed [5 + 2] allenyl-vinylcyclopropane cycloaddition. The key cycloaddition precursor is convergently assembled from (R)-(+)-limonene and cyclopropane diester through a novel decarboxylative dehydration reaction. The metal-catalyzed [5 + 2] cycloaddition of this precursor proceeds with complete chemo, endo/exo, and diastereoselectivity in 93% yield, representing an effective general route to bicyclo[5.3.0]decane derivatives.

Publication types

Research Support, Non-U.S. Gov't
Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Alkadienes / chemistry*
Alkadienes / metabolism
Azulenes
Cycloheptanes / chemistry*
Cycloheptanes / metabolism
Cyclohexenes
Cyclopropanes / chemistry
Cyclopropanes / metabolism
Fruit / chemistry
Limonene
Polycyclic Compounds / chemical synthesis
Polycyclic Compounds / chemistry
Polycyclic Compounds / metabolism
Sesquiterpenes / chemical synthesis*
Sesquiterpenes / chemistry
Sesquiterpenes / metabolism
Sesquiterpenes / toxicity
Stereoisomerism
Terpenes / metabolism

Substances

Alkadienes
Azulenes
Cycloheptanes
Cyclohexenes
Cyclopropanes
Polycyclic Compounds
Sesquiterpenes
Terpenes
aphanamol I
propadiene
azulene
cyclopropane
Limonene