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Catalyst-Controlled Selective Functionalization of Unactivated C–H Bonds in the Presence of Electronically Activated C–H Bonds

Liu, Wenbin and Ren, Zhi and Bosse, Aaron T. and Liao, Kuangbiao and Goldstein, Elizabeth L. and Bacsa, John and Musaev, Djamaladdin G. and Stoltz, Brian M. and Davies, Huw M. L. (2018) Catalyst-Controlled Selective Functionalization of Unactivated C–H Bonds in the Presence of Electronically Activated C–H Bonds. Journal of the American Chemical Society, 140 (38). pp. 12247-12255. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20180917-125103681

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Abstract

A new chiral dirhodium tetracarboxylate catalyst, Rh_2(S-2-Cl-5-BrTPCP)_4, has been developed for C–H functionalization reactions by means of donor/acceptor carbene intermediates. The dirhodium catalyst contains four (S)-1-(2-chloro-5-bromophenyl)-2,2-diphenylcyclopropane-1-carboxylate ligands, in which all four 2-chloro-5-bromophenyl groups are on the same face of the catalyst, leading to a structure, which is close to C_4 symmetric. The catalyst induces highly site selective functionalization of remote, unactivated methylene C–H bonds even in the presence of electronically activated benzylic C–H bonds, which are typically favored using earlier established dirhodium catalysts, and the reactions proceed with high levels of diastereo- and enantioselectivity. This C–H functionalization method is applicable to a variety of aryl and heteroaryl derivatives. Furthermore, the potential of this methodology was illustrated by sequential C–H functionalization reactions to access the macrocyclic core of the cylindrocyclophane class of natural products.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/jacs.8b07534DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/jacs.8b07534PublisherSupporting Information
ORCID:
AuthorORCID
Liu, Wenbin0000-0001-8854-8174
Ren, Zhi0000-0001-9812-0251
Musaev, Djamaladdin G.0000-0003-1160-6131
Stoltz, Brian M.0000-0001-9837-1528
Davies, Huw M. L.0000-0001-6254-9398
Additional Information:© 2018 American Chemical Society. Received: July 24, 2018. Publication Date (Web): September 17, 2018. We thank Dr. LaDena A. Bolton for preliminary studies on the thiophene derivatized substrates. Financial support was provided by NSF under the CCI Center for Selective C–H Functionalization (CHE-1700982). E.L.G. recognizes the NSF for a predoctoral research fellowship (No. DGE-1745301). D.G.M. acknowledges an NSF MRI-R2 Grant (CHE-0958205) and the use of the resources of the Cherry Emerson Center for Scientific Computation. Funds to purchase the NMR and X-ray spectrometers used in these studies were supported by the NSF (CHE 1531620 and CHE 1626172). The authors declare the following competing financial interest(s): HMLD is a named inventor on a patent entitled, Dirhodium Catalyst Compositions and Synthetic Processes Related There-to (US 8,974,428, issued March 10, 2015). The other authors have no competing financial interests.
Funders:
Funding AgencyGrant Number
NSFCHE-1700982
NSF Graduate Research FellowshipDGE-1745301
NSFCHE-0958205
NSFCHE-1531620
NSFCHE-1626172
Record Number:CaltechAUTHORS:20180917-125103681
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180917-125103681
Official Citation:Catalyst-Controlled Selective Functionalization of Unactivated C–H Bonds in the Presence of Electronically Activated C–H Bonds Wenbin Liu, Zhi Ren, Aaron T. Bosse, Kuangbiao Liao, Elizabeth L. Goldstein, John Bacsa, Djamaladdin G. Musaev, Brian M. Stoltz, and Huw M. L. Davies Journal of the American Chemical Society 2018 140 (38), 12247-12255 DOI: 10.1021/jacs.8b07534
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:89676
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:17 Sep 2018 20:22
Last Modified:01 Oct 2018 18:15

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