Synlett 2014; 25(4): 591-595
DOI: 10.1055/s-0033-1340471
letter
© Georg Thieme Verlag Stuttgart · New York

Synthetic and Mechanistic Aspects on the Competition between C–H Insertion and Hydride Transfer in Copper-Mediated Transformations of α-Diazo-β-Keto Sulfones

Catherine N. Slattery
a   Department of Chemistry, Analytical and Biological Research Facility, University College Cork, Cork, Ireland
,
Alan Ford
a   Department of Chemistry, Analytical and Biological Research Facility, University College Cork, Cork, Ireland
,
Kevin S. Eccles
b   Department of Chemistry, School of Pharmacy, Synthesis and Solid State Pharmaceutical Centre, Analytical and Biological Research Facility, University College Cork, Cork, Ireland   Fax: +353(21)4274097   Email: a.maguire@ucc.ie
,
Simon E. Lawrence
b   Department of Chemistry, School of Pharmacy, Synthesis and Solid State Pharmaceutical Centre, Analytical and Biological Research Facility, University College Cork, Cork, Ireland   Fax: +353(21)4274097   Email: a.maguire@ucc.ie
,
Anita R. Maguire*
b   Department of Chemistry, School of Pharmacy, Synthesis and Solid State Pharmaceutical Centre, Analytical and Biological Research Facility, University College Cork, Cork, Ireland   Fax: +353(21)4274097   Email: a.maguire@ucc.ie
› Author Affiliations
Further Information

Publication History

Received: 06 November 2013

Accepted: 23 November 2013

Publication Date:
08 January 2014 (online)


Abstract

Competition between C–H insertion and hydride transfer is reported for the copper-catalysed reactions of a range of phenyl-substituted α-diazo-β-keto sulfones. Control of chemoselectivity is possible by alteration of the electronic properties of the diazo substrate. The production of enantioenriched cyclopentanones (up to 89% ee), formed via C–H insertion, and alkylidene tetrahydrofurans (up to 43% ee), produced via hydride transfer, is described. The isolation of products derived from hydride transfer provides mechanistic insight into the copper-mediated C–H insertion of α-diazo­carbonyl compounds.

Supporting Information

Primary Data