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Direct Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones

Martinez Alvarado, Jesus I. and Ertel, Alyssa B. and Stegner, Andrea and Stache, Erin E. and Doyle, Abigail G. (2019) Direct Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones. Organic Letters, 21 (24). pp. 9940-9944. ISSN 1523-7060. https://resolver.caltech.edu/CaltechAUTHORS:20200116-094012400

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Abstract

A general protocol for the hydroacylation of styrenes from aliphatic carboxylic acids is reported. These reactions proceed via β-scission of a phosphoranyl radical that is accessed by photoredox catalysis, followed by addition of the resulting acyl radical to the styrenyl olefin. We show that phosphine tunability is critical for efficient intermolecular coupling due to competitive quenching of the photocatalyst by the olefin. Primary, secondary, and structurally rigid tertiary carboxylic acids all generate valuable unsymmetrical dialkyl ketones.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.orglett.9b03871DOIArticle
ORCID:
AuthorORCID
Doyle, Abigail G.0000-0002-6641-0833
Additional Information:© 2019 American Chemical Society. Received: October 30, 2019; Published: November 21, 2019. We thank the MacMillan lab (Princeton University) for access to their photoreactors and Lotus Separations for assistance with a purification. Financial support for this project was provided by NIGMS R35 GM126986. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NIHR35 GM126986
Issue or Number:24
Record Number:CaltechAUTHORS:20200116-094012400
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200116-094012400
Official Citation:Direct Use of Carboxylic Acids in the Photocatalytic Hydroacylation of Styrenes To Generate Dialkyl Ketones. Jesus I. Martinez Alvarado, Alyssa B. Ertel, Andrea Stegner, Erin E. Stache, and Abigail G. Doyle. Organic Letters 2019 21 (24), 9940-9944; DOI: 10.1021/acs.orglett.9b03871
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:100755
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 Jan 2020 17:59
Last Modified:16 Jan 2020 17:59

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