Copper‐Catalyzed C(sp 3 )−H Amidation: Sterically Driven Primary and Secondary C−H Site‐Selectivity

Bakhoda, Abolghasem (Gus); Jiang, Quan; Badiei, Yosra M.; Bertke, Jeffery A.; Cundari, Thomas R.; Warren, Timothy H.

doi:10.1002/anie.201810556

Copper‐Catalyzed C(sp ³ )−H Amidation: Sterically Driven Primary and Secondary C−H Site‐Selectivity

Journal Article · Thu Feb 07 00:00:00 EST 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201810556· OSTI ID:1493862

Bakhoda, Abolghasem (Gus) ^[1]; Jiang, Quan ^[2]; Badiei, Yosra M. ^[1]; Bertke, Jeffery A. ^[1]; Cundari, Thomas R. ^[2]; ^[1]

Department of Chemistry Georgetown University Box 571227 Washington DC 20057-1227 USA
Department of Chemistry Center for Advanced Scientific Computing and Modeling (CASCaM) University of North Texas Denton TX 76203 USA

Abstract

Undirected C(sp ³ )−H functionalization reactions often follow site‐selectivity patterns that mirror the corresponding C−H bond dissociation energies (BDEs). This often results in the functionalization of weaker tertiary C−H bonds in the presence of stronger secondary and primary bonds. An important, contemporary challenge is the development of catalyst systems capable of selectively functionalizing stronger primary and secondary C−H bonds over tertiary and benzylic C−H sites. Herein, we report a Cu catalyst that exhibits a high degree of primary and secondary over tertiary C−H bond selectivity in the amidation of linear and cyclic hydrocarbons with aroyl azides ArC(O)N ₃ . Mechanistic and DFT studies indicate that C−H amidation involves H‐atom abstraction from R‐H substrates by nitrene intermediates [Cu](κ ² ‐ N , O ‐NC(O)Ar) to provide carbon‐based radicals R ^. and copper(II)amide intermediates [Cu ^II ]‐NHC(O)Ar that subsequently capture radicals R ^. to form products R‐NHC(O)Ar. These studies reveal important catalyst features required to achieve primary and secondary C−H amidation selectivity in the absence of directing groups.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15387

OSTI ID:: 1493862

Alternate ID(s):: OSTI ID: 1609409

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 11 Vol. 58; ISSN 1433-7851

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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