Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation

Shockley, Samantha E. and Hethcox, J. Caleb and Stoltz, Brian M. (2017) Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives through Iridium-Catalyzed Allylic Alkylation. Angewandte Chemie International Edition, 56 (38). pp. 11545-11548. ISSN 1433-7851. PMCID PMC5674796. doi:10.1002/anie.201707015. https://resolver.caltech.edu/CaltechAUTHORS:20170719-091950600

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Abstract

The first highly enantioselective iridium-catalyzed allylic alkylation providing access to products bearing an allylic all-carbon quaternary stereogenic center has been developed. The reaction utilizes a masked acyl cyanide (MAC) reagent, which enables the one-pot preparation of α-quaternary carboxylic acids, esters, and amides with a high degree of enantioselectivity. The utility of these products is further explored via a series of diverse product transformations.

Item Type:

Article

Related URLs:

URL	URL Type	Description
https://doi.org/10.1002/anie.201707015	DOI	Article
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5674796	PubMed Central	Article

ORCID:

Author	ORCID
Shockley, Samantha E.	0000-0001-5682-8569
Hethcox, J. Caleb	0000-0002-7712-308X
Stoltz, Brian M.	0000-0001-9837-1528

Alternate Title:

Enantioselective Synthesis of Acyclic α-Quaternary Carboxylic Acid Derivatives via Iridium-Catalyzed Allylic Alkylation

Additional Information:

© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: July 10, 2017; Accepted manuscript online: July 19, 2017; Version of record online: August 9, 2017. The NIH-NIGMS (R01GM080269) and Caltech are thanked for support of our research program. J.C.H. thanks the Camille and Henry Dreyfus postdoctoral program, and S.E.S. thanks the NIH-NIGMS for a predoctoral fellowship (F31GM120804). Dr. Michael Takase, Dr. Lawrence Henling, and Niklas Thompson are acknowledged for assistance with X-ray analysis. Dr. Mona Shahgholi and Naseem Torian are thanked for mass spectrometry assistance. Dr. Scott Virgil is thanked for assistance with instrumentation. The authors declare no conflict of interest.

Funders:

Funding Agency	Grant Number
NIH	R01GM080269
Caltech	UNSPECIFIED
Camille and Henry Dreyfus Foundation	UNSPECIFIED
NIH Predoctoral Fellowship	F31GM120804

Subject Keywords:

allylic alkylation; carboxylic acid derivatives; iridium; quaternary stereocenter; umpolung

Issue or Number:

PubMed Central ID:

PMC5674796

DOI:

10.1002/anie.201707015

Record Number:

CaltechAUTHORS:20170719-091950600

Persistent URL:

https://resolver.caltech.edu/CaltechAUTHORS:20170719-091950600

Official Citation:

S. E. Shockley, J. C. Hethcox, B. M. Stoltz, Angew. Chem. Int. Ed. 2017, 56, 11545

Usage Policy:

No commercial reproduction, distribution, display or performance rights in this work are provided.

ID Code:

79196

Collection:

CaltechAUTHORS

Deposited By:

Tony Diaz

Deposited On:

19 Jul 2017 16:29

Last Modified:

23 Mar 2022 19:48

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