Synlett 2015; 26(04): 494-500
DOI: 10.1055/s-0034-1379882
letter
© Georg Thieme Verlag Stuttgart · New York

Insight into the Copper-Catalyzed Borylation of Strained Alkenes

Alejandro Parra
Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain   Email: mariola.tortosa@uam.es
,
Aurora López
Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain   Email: mariola.tortosa@uam.es
,
Sergio Díaz-Tendero
Departamento de Química (módulo 13), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain
,
Laura Amenós
Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain   Email: mariola.tortosa@uam.es
,
José Luis García Ruano
Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain   Email: mariola.tortosa@uam.es
,
Mariola Tortosa*
Departamento de Química Orgánica (módulo 01), Universidad Autónoma de Madrid, Cantoblanco, 28049 Madrid, Spain   Email: mariola.tortosa@uam.es
› Author Affiliations
Further Information

Publication History

Received: 02 November 2014

Accepted: 26 November 2014

Publication Date:
09 January 2015 (eFirst)

Abstract

The copper-catalyzed hydro- and carboboration of strained alkenes is presented. The reaction is highly diastereoselective and affords boronic ester derivatives many of which are difficult to synthesize by known methods. Competition experiments with different alkenes show that high levels of chemoselectivity can be achieved. Density functional theory calculations are in agreement with the observed chemoselectivity.

Supporting Information

 
  • References and Notes

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  • 11 We selected compounds 1a, 1c, 1d, and 1e to study the influence of the ring strain and the bridgehead atom in the copper–boryl complex insertion. We did not include azabenzonorbornadiene 1b in the competition study because additional steric effects from the tosyl group, not present in the other bicycles, could also affect the reactivity.
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