One-pot zinc-promoted asymmetric alkynylation/brook-type rearrangement/ene-allene cyclization: highly selective formation of three new bonds and two stereocenters in acyclic systems

Polina Smirnov; Jomon Mathew; Anne Nijs; Einat Katan; Miriam Karni; Carsten Bolm; Yitzhak Apeloig; Ilan Marek

doi:10.1002/anie.201306749

One-pot zinc-promoted asymmetric alkynylation/brook-type rearrangement/ene-allene cyclization: highly selective formation of three new bonds and two stereocenters in acyclic systems

Angew Chem Int Ed Engl. 2013 Dec 16;52(51):13717-21. doi: 10.1002/anie.201306749. Epub 2013 Oct 23.

Authors

Polina Smirnov¹, Jomon Mathew, Anne Nijs, Einat Katan, Miriam Karni, Carsten Bolm, Yitzhak Apeloig, Ilan Marek

Affiliation

¹ Schulich Faculty of Chemistry and the Lise Meitner-Minerva Center for Computational Quantum Chemistry, Technion-Israel Institute of Technology, Technion City, Haifa 32000 (Israel).

PMID: 24155160
DOI: 10.1002/anie.201306749

Abstract

It's as easy as 1, 2, 3: In a one-pot sequence, two stereocenters and three new bonds were created with high selectivity through an asymmetric alkynylation of acyl silanes, a tandem Brook-type rearrangement and Zn-ene-allene cyclization, the addition of an electrophile, and finally oxidation. The straightforward nature of the synthetic procedure contrasts strongly with the complexity of the densely functionalized products obtained.

Keywords: Brook rearrangement; acyl silanes; alkynylation; asymmetric synthesis; zinc.