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Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation

Hethcox, J. Caleb and Shockley, Samantha E. and Stoltz, Brian M. (2018) Enantioselective Synthesis of Vicinal All-Carbon Quaternary Centers via Iridium-Catalyzed Allylic Alkylation. Angewandte Chemie International Edition, 57 (28). pp. 8664-8667. ISSN 1433-7851. PMCID PMC6033654. https://resolver.caltech.edu/CaltechAUTHORS:20180514-112203501

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Abstract

The development of the first enantioselective transition‐metal‐catalyzed allylic alkylation providing access to acyclic products bearing vicinal all‐carbon quaternary centers is disclosed. The iridium‐catalyzed allylic alkylation reaction proceeds with excellent yields and selectivities for a range of malononitrile‐derived nucleophiles and trisubstituted allylic electrophiles. The utility of these sterically congested products is explored through a series of diverse chemo‐ and diastereoselective product transformations to afford a number of highly valuable, densely functionalized building blocks, including those containing vicinal all‐carbon quaternary stereocenters.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.201804820DOIArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6033654/PubMed CentralArticle
ORCID:
AuthorORCID
Hethcox, J. Caleb0000-0002-7712-308X
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2018 Wiley‐VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: April 25, 2018; Accepted manuscript online: May 11, 2018; Version of record online: June 11, 2018. 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 and Dr. Lawrence Henling are acknowledge for assistance with X-ray analysis. Dr. Mona Shahgholi and Naseem Torian are thanked for mass spectrometry assistance. Dr. David VanderVelde is thanked for assistance with NMR analysis.
Funders:
Funding AgencyGrant Number
NIHR01GM080269
CaltechUNSPECIFIED
Camille and Henry Dreyfus FoundationUNSPECIFIED
NIH Predoctoral FellowshipF31GM120804
Issue or Number:28
PubMed Central ID:PMC6033654
Record Number:CaltechAUTHORS:20180514-112203501
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180514-112203501
Official Citation:J. C. Hethcox, S. E. Shockley, B. M. Stoltz, Angew. Chem. Int. Ed. 2018, 57, 8664
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86392
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:16 May 2018 16:47
Last Modified:09 Mar 2020 13:18

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