HFIP Mediates a Direct C-C Coupling between Michael Acceptors and Eschenmoser's salt

Miran Lemmerer; Margaux Riomet; Ricardo Meyrelles; Boris Maryasin; Leticia González; Nuno Maulide

doi:10.1002/anie.202109933

HFIP Mediates a Direct C-C Coupling between Michael Acceptors and Eschenmoser's salt

Angew Chem Int Ed Engl. 2022 Mar 7;61(11):e202109933. doi: 10.1002/anie.202109933. Epub 2022 Feb 3.

Authors

Miran Lemmerer¹, Margaux Riomet¹, Ricardo Meyrelles^{1

2}, Boris Maryasin^{1

2}, Leticia González², Nuno Maulide¹

Affiliations

¹ Institute of Organic Chemistry, University of Vienna, Währinger Strasse 38, 1090, Vienna, Austria.
² Institute of Theoretical Chemistry, University of Vienna, Währinger Strasse 17, 1090, Vienna, Austria.

Abstract

A direct C-C coupling process that merges Michael acceptors and Eschenmoser's salt is presented. Although reminiscent of the Morita-Baylis-Hillman reaction, this process requires no Lewis base catalyst. The underlying mechanism was unveiled by a combination of kinetic, isotopic labelling experiments as well as computational investigations, which showcased the critical role of HFIP as a superior mediator for proton-transfer events as well as the decisive role of the halide counterion.

Keywords: Amines; Hydrogen bonds; Iodine; Quantum chemistry; Solvent effects.

Publication types

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

Grants and funding

P 30226/FWF_/Austrian Science Fund FWF/Austria