CaltechAUTHORS
  A Caltech Library Service

Palladium(II)-Catalyzed Allylic C-H Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation

Xing, Xiangyou and O'Connor, Nicholas R. and Stoltz, Brian M. (2015) Palladium(II)-Catalyzed Allylic C-H Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation. Angewandte Chemie International Edition, 54 (38). pp. 11186-11190. ISSN 1433-7851. https://resolver.caltech.edu/CaltechAUTHORS:20150807-090520766

[img] PDF - Published Version
Restricted to Caltech community only
See Usage Policy.

809Kb
[img] PDF - Supplemental Material
See Usage Policy.

9Mb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20150807-090520766

Abstract

The use of Oxone and a palladium(II) catalyst enables the efficient allylic C-H oxidation of sterically hindered α-quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for C-H activation allows for unusual tunable selectivity between a two-electron oxidation to the allylic acetates and a four-electron oxidation to the corresponding enals, with the dominant product depending on the presence or absence of water. The versatile synthetic utility of both the allylic acetate and enal products accessible through this methodology is also demonstrated.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1002/anie.201504007DOIArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201504007/abstractPublisherArticle
http://onlinelibrary.wiley.com/doi/10.1002/anie.201504007/suppinfoPublisherSupporting Information
ORCID:
AuthorORCID
Stoltz, Brian M.0000-0001-9837-1528
Additional Information:© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Received: May 5, 2015; Revised: June 23, 2015; Article first published online: 31 Jul 2015. This work was supported by the NSF under the CCI Center for Selective C-H Functionalization, CHE-1205646. Additional support was provided by Caltech and Amgen. Dr. Scott C. Virgil is thanked for helpful discussions. Dr. David VanderVelde (NMR), Dr. Michael K. Takase (X-ray crystallography), and Dr. Mona Shahgholi (HRMS) are acknowledged for assistance with structural determination and characterization. Guillermo A. Guerrero-Vásquez, Lukas J. Hilpert, and Dr. Wen-Bo Liu are acknowledged for experimental assistance.
Group:CCI Solar Fuels
Funders:
Funding AgencyGrant Number
NSFCHE-1205646
CaltechUNSPECIFIED
AmgenUNSPECIFIED
Subject Keywords:allylic compounds; C-H functionalization; heterocycles; oxidation; palladium
Issue or Number:38
Record Number:CaltechAUTHORS:20150807-090520766
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20150807-090520766
Official Citation:Xing, X., O'Connor, N. R. and Stoltz, B. M. (2015), Palladium(II)-Catalyzed Allylic C[BOND]H Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation. Angew. Chem. Int. Ed., 54: 11186–11190. doi:10.1002/anie.201504007
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:59302
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:07 Aug 2015 16:32
Last Modified:03 Oct 2019 08:45

Repository Staff Only: item control page