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Pd-catalyzed Fukuyama cross-coupling of secondary organozinc reagents for the direct synthesis of unsymmetrical ketones

Cherney, Alan H. and Reisman, Sarah E. (2014) Pd-catalyzed Fukuyama cross-coupling of secondary organozinc reagents for the direct synthesis of unsymmetrical ketones. Tetrahedron, 70 (20). pp. 3259-3265. ISSN 0040-4020. doi:10.1016/j.tet.2013.11.104. https://resolver.caltech.edu/CaltechAUTHORS:20140113-100609164

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Abstract

The coupling of acyl electrophiles with organometallic reagents represents a convergent route toward complex and versatile ketone products. Despite the mild conditions and high functional group tolerance, the cross-coupling of carboxylic acid derivatives, such as thioesters, and secondary organometallic reagents is an underdeveloped transformation. Herein, we disclose a convenient and efficient protocol for the Pd-catalyzed Fukuyama cross-coupling of secondary organozinc reagents with thioester electrophiles. Under these mild conditions, a range of thioesters possessing sensitive functional groups can be coupled with either activated or unactivated secondary organozinc halides in good yields. This method was expanded to include an acid chloride substrate, generating an aryl alkyl ketone in high yield. In addition, a modest dynamic kinetic resolution of the organozinc reagent can be achieved using chiral phosphoramidite ligands to furnish enantioenriched ketone products.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/j.tet.2013.11.104DOIArticle
http://www.sciencedirect.com/science/article/pii/S0040402013018371PublisherArticle
ORCID:
AuthorORCID
Cherney, Alan H.0000-0001-7440-6634
Reisman, Sarah E.0000-0001-8244-9300
Additional Information:© 2013 Elsevier Ltd. Received 26 August 2013. Received in revised form 21 November 2013. Accepted 29 November 2013. Available online 7 December 2013. We thank Prof. Brian Stoltz, Dr. Scott Virgil, and the Caltech Center for Catalysis and Chemical Synthesis for access to analytical equipment. We also thank Sigma-Aldrich for a kind donation of chemicals. Fellowship support was provided by the National Science Foundation (Graduate Research Fellowship, A.H.C., Grant No. DGE-1144469). S.E.R. is a fellow of the Alfred P. Sloan Foundation, a Camille Dreyfus Teacher-Scholar, and an American Cancer Society Research Scholar. Financial support from the California Institute of Technology, Amgen, DuPont, Novartis, Boehringer Ingelheim, and the National Science Foundation (CAREER-1057143) is gratefully acknowledged.
Funders:
Funding AgencyGrant Number
NSF Graduate Research FellowshipDGE-1144469
CaltechUNSPECIFIED
AmgenUNSPECIFIED
DuPontUNSPECIFIED
NovartisUNSPECIFIED
Boehringer-IngelheimUNSPECIFIED
NSFCHE-1057143
Subject Keywords: Palladium; Cross-coupling; Organozinc
Issue or Number:20
DOI:10.1016/j.tet.2013.11.104
Record Number:CaltechAUTHORS:20140113-100609164
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140113-100609164
Official Citation:Alan H. Cherney, Sarah E. Reisman, Pd-catalyzed Fukuyama cross-coupling of secondary organozinc reagents for the direct synthesis of unsymmetrical ketones, Tetrahedron, Volume 70, Issue 20, 20 May 2014, Pages 3259-3265, ISSN 0040-4020, http://dx.doi.org/10.1016/j.tet.2013.11.104. (http://www.sciencedirect.com/science/article/pii/S0040402013018371)
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43334
Collection:CaltechAUTHORS
Deposited By:INVALID USER
Deposited On:13 Jan 2014 18:27
Last Modified:10 Nov 2021 16:36

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