Catalytic SN2'- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

Ying Shi; Amir H Hoveyda

doi:10.1002/anie.201600309

Catalytic SN2'- and Enantioselective Allylic Substitution with a Diborylmethane Reagent and Application in Synthesis

Angew Chem Int Ed Engl. 2016 Mar 1;55(10):3455-8. doi: 10.1002/anie.201600309. Epub 2016 Feb 4.

Authors

Ying Shi¹, Amir H Hoveyda²

Affiliations

¹ Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA.
² Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA, 02467, USA. amir.hoveyda@bc.edu.

Abstract

A catalytic method for the site- and enantioselective addition of commercially available di-B(pin)-methane to allylic phosphates is introduced (pin=pinacolato). Transformations may be facilitated by an NHC-Cu complex (NHC=N-heterocyclic carbene) and products obtained in 63-95 % yield, 88:12 to >98:2 S(N)2'/S(N)2 selectivity, and 85:15-99:1 enantiomeric ratio. The utility of the approach, entailing the involvement of different catalytic cross-coupling processes, is highlighted by its application to the formal synthesis of the cytotoxic natural product rhopaloic acid A.

Keywords: N-heterocyclic carbenes; allylic substitution; boron; copper; enantioselective synthesis.

Publication types

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

MeSH terms

Boron Compounds / chemistry*
Catalysis
Indicators and Reagents / chemistry*
Stereoisomerism

Substances

Boron Compounds
Indicators and Reagents

Abstract

Publication types

MeSH terms

Substances

Grants and funding