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Published September 26, 2018 | Supplemental Material
Journal Article Open

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


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.

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.

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Supplemental Material - ja8b07534_si_002.cif

Supplemental Material - ja8b07534_si_003.cif

Supplemental Material - ja8b07534_si_004.cif

Supplemental Material - ja8b07534_si_005.cif

Supplemental Material - ja8b07534_si_006.cif


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August 19, 2023
October 18, 2023