Work

H· Transfer-Initiated Synthesis of γ-Lactams: Interpretation of Cycloisomerization and Hydrogenation Ratios

Year: 2019

Type: article

Abstract: A cobaloxime/H 2 system used to synthesize valuable γ-lactams from acrylamide molecules is described. In addition to cycloisomerized lactams, linear hydrogenated products were also observed. The amounts of the hydrogenation product were observed to correlate with the bulk of the substituent on the acrylamide nitrogen. Further analysis of the product distributions with experimental and computational studies suggested that while cyclization can occur from one C═C acrylamide rotamer, hydrogenation can occur from both. This observation was further evinced through calculation of the hydrogenation rate constant, which was observed to be ca. 10 2 faster than previously determined for a related system using n Bu 3 SnH.

Source: ACS Catalysis

DOI: 10.1021/acscatal.9b03678

Authors: Chris Lorenc, Hunter B. Vibbert, Chengbo Yao, Jack R. Norton, Michael Rauch

Institution: Columbia University

Language: English

Topic: Organometallic Complex Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funder: National Institute of General Medical Sciences

Award: Catalysis of Tin-Free Radical Reactions Under H2