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Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation

Kim, Kelly E. and Li, Jiaming and Grubbs, Robert H. and Stoltz, Brian M. (2016) Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation. Journal of the American Chemical Society, 138 (40). pp. 13179-13182. ISSN 0002-7863. doi:10.1021/jacs.6b08788. https://resolver.caltech.edu/CaltechAUTHORS:20161003-161852128

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Abstract

A new strategy for the functionalization of sterically hindered terminal olefins is reported. Alkenes bearing quaternary carbons at the allylic or homoallylic position are readily oxidized to the corresponding aldehydes by palladium/copper/nitrite catalysis. A broad range of functional groups including esters, nitriles, silyl ethers, vinylogous esters, ketones, lactones, and β-ketoesters are tolerated under the reaction conditions. The crude aldehyde products can be transformed further, enabling direct conversion of hindered terminal alkenes to various other synthetically useful functional groups, resulting in formal anti-Markovnikov hydroamination, among other transformations.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jacs.6b08788DOIArticle
http://pubs.acs.org/doi/abs/10.1021/jacs.6b08788PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/jacs.6b08788PublisherSupporting Information
ORCID:
AuthorORCID
Li, Jiaming0000-0001-6646-5693
Grubbs, Robert H.0000-0002-0057-7817
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2016 American Chemical Society. Received: August 25, 2016. Publication Date (Web): September 27, 2016. This manuscript is dedicated to Professor Samuel J. Danishefsky on the occasion of his 80th birthday. This work was supported by the NSF under the CCI Center for Selective C–H Functionalization, CHE-1205646. Additional financial support was provided by Caltech and Novartis. Dr. Mona Shahgholi and Naseem Torian are acknowledged for assistance with high-resolution mass spectrometry. Dr. Yiyang Liu, Nicholas R. O’Connor, Dr. Allen Y. Hong, and Prof. Wen-Bo Liu are acknowledged for contributions to substrate preparation. Beau P. Pritchett is thanked for preparation of the Ohira–Bestmann reagent. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1205646
CaltechUNSPECIFIED
NovartisUNSPECIFIED
Issue or Number:40
DOI:10.1021/jacs.6b08788
Record Number:CaltechAUTHORS:20161003-161852128
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20161003-161852128
Official Citation:Catalytic Anti-Markovnikov Transformations of Hindered Terminal Alkenes Enabled by Aldehyde-Selective Wacker-Type Oxidation Kelly E. Kim, Jiaming Li, Robert H. Grubbs, and Brian M. Stoltz Journal of the American Chemical Society 2016 138 (40), 13179-13182 DOI: 10.1021/jacs.6b08788
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:70776
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:04 Oct 2016 14:39
Last Modified:11 Nov 2021 04:34

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