Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H2 : A Catalytic and Mechanistic Study

Subrata Chakraborty; Urs Gellrich; Yael Diskin-Posner; Gregory Leitus; Liat Avram; David Milstein

doi:10.1002/anie.201700681

Manganese-Catalyzed N-Formylation of Amines by Methanol Liberating H₂ : A Catalytic and Mechanistic Study

Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4229-4233. doi: 10.1002/anie.201700681. Epub 2017 Mar 20.

Authors

Subrata Chakraborty¹, Urs Gellrich¹, Yael Diskin-Posner², Gregory Leitus², Liat Avram², David Milstein¹

Affiliations

¹ Department of Organic Chemistry, Weizmann Institute of Science, Rehovot, 76100, Israel.
² Chemical Research Support, Weizmann Institute of Science, Rehovot, 76100, Israel.

PMID: 28319299
DOI: 10.1002/anie.201700681

Abstract

The first example of a base metal (manganese) catalyzed acceptorless dehydrogenative coupling of methanol and amines to form formamides is reported herein. The novel pincer complex (iPr-PN^H P)Mn(H)(CO)₂ catalyzes the reaction under mild conditions in the absence of any additives, bases, or hydrogen acceptors. Mechanistic insight based on the observation of an intermediate and DFT calculations is also provided.

Keywords: dehydrogenation; formylation; manganese; methanol; pincer complexes.

Publication types

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