Synthetic and mechanistic studies of the aza-retro-Claisen rearrangement. A facile route to medium ring nitrogen heterocycles

Robert K Boeckman Jr; Nathan E Genung; Ke Chen; Todd R Ryder

doi:10.1021/ol100397q

Synthetic and mechanistic studies of the aza-retro-Claisen rearrangement. A facile route to medium ring nitrogen heterocycles

Org Lett. 2010 Apr 2;12(7):1628-31. doi: 10.1021/ol100397q.

Authors

Robert K Boeckman Jr¹, Nathan E Genung, Ke Chen, Todd R Ryder

Affiliation

¹ Department of Chemistry, University of Rochester, Rochester, New York 14627-0216, USA. rkb@rkbmac.chem.rochester.edu

PMID: 20218707
DOI: 10.1021/ol100397q

Abstract

An efficient synthesis of medium-sized heterocyclic rings was achieved using a one-pot aza-Wittig/retro-aza-Claisen sequence of vinyl cyclobutanecarboxaldehydes derived from simple allylic carbonates. The use of various Staudinger reagents in the aza-Wittig reaction allows for a variety of N-substituted products to be obtained. The rearrangement is under thermodynamic control driven by relief of the cyclobutane ring strain and resonance stabilization of the resulting vinylogous amide/sulfonamide.

Publication types

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

MeSH terms

Aza Compounds / chemical synthesis*
Aza Compounds / chemistry
Cyclization
Heterocyclic Compounds / chemical synthesis*
Heterocyclic Compounds / chemistry
Molecular Structure
Stereoisomerism
Thermodynamics

Substances

Aza Compounds
Heterocyclic Compounds