Gold(I)-Assisted α-Allylation of Enals and Enones with Alcohols

Marco Michele Mastandrea; Niall Mellonie; Pietro Giacinto; Alba Collado; Steven P Nolan; Gian Pietro Miscione; Andrea Bottoni; Marco Bandini

doi:10.1002/anie.201507218

Gold(I)-Assisted α-Allylation of Enals and Enones with Alcohols

Angew Chem Int Ed Engl. 2015 Dec 1;54(49):14885-9. doi: 10.1002/anie.201507218. Epub 2015 Oct 16.

Authors

Marco Michele Mastandrea¹, Niall Mellonie¹, Pietro Giacinto¹, Alba Collado², Steven P Nolan^{2

3}, Gian Pietro Miscione^{1

4}, Andrea Bottoni¹, Marco Bandini⁵

Affiliations

¹ Department of Chemistry "G. Ciamician", Alma Mater Studiorum-University of Bologna, via Selmi 2, 40126, Bologna (Italy).
² EaStCHEM School of Chemistry, University of St. Andrews, St. Andrews, KY16 9ST (UK).
³ Chemistry Department, College of Science, King Saud University, Riyadh 11451 (Saudi Arabia).
⁴ Department of Chemistry, Universidad de los Andes, Carrera 1 N° 18A 10, Bogotá (Colombia).
⁵ Department of Chemistry "G. Ciamician", Alma Mater Studiorum-University of Bologna, via Selmi 2, 40126, Bologna (Italy). marco.bandini@unibo.it.

PMID: 26473619
DOI: 10.1002/anie.201507218

Abstract

The intermolecular α-allylation of enals and enones occurs by the condensation of variously substituted allenamides with allylic alcohols. Cooperative catalysis by [Au(ItBu)NTf2] and AgNTf2 enables the synthesis of a range of densely functionalized α-allylated enals, enones, and acyl silanes in good yield under mild reaction conditions. DFT calculations support the role of an α-gold(I) enal/enone as the active nucleophilic species.

Keywords: alcohols; allylation; gold catalysis; reaction mechanisms; unsaturated carbonyl compounds.

Publication types

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