Palladium-Catalyzed Aminocarbonylation of Aryl Chlorides at Atmospheric Pressure: The Dual Role of Sodium Phenoxide

Authors

  • Joseph R. Martinelli Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave. Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297
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  • Thomas P. Clark Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave. Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297
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  • Donald A. Watson Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave. Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297
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  • Rachel H. Munday Dr.,

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave. Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297
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  • Stephen L. Buchwald Prof. Dr.

    1. Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Ave. Cambridge, MA 02139, USA, Fax: (+1) 617-253-3297
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  • We thank the National Institutes of Health (GM46059) and the MIT–Singapore Alliance for funding. We are indebted to Merck, Amgen, and Boehringer-Ingelheim for unrestricted support. We are also extremely grateful to Nippon Chemical Co. for providing generous donations of 68. We also thank BASF for a donation of palladium acetate.

Abstract

original image

No pressure, no worries: A general, functional-group-tolerant, mild system for the Pd-catalyzed carbonylation of aryl chlorides to the corresponding amides has been developed. The catalyst operates at 1 atm CO using an inexpensive, air-stable, and commercially available ligand (see scheme, Cy=cyclohexyl). Sodium phenoxide is a critical additive in this transformation; its role has been studied using in situ IR spectroscopy.

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