Vicinal disubstitution of alkyl C–X synthons via alkene radical cation generation
Abstract
In organic chemistry, functionalization of two adjacent carbons often starts from alkenes or already disubstituted precursors. Herein, we report an exergonic activation mode that directly generates alkene radical cation intermediates from monofunctional C(sp 3 )–X handles through a photoredox-triggered hydrogen-atom abstraction (HAT) and spin-center shift (SCS) process. Computations show that electron delocalization and a network of hydrogen-bonding solvent molecules facilitate a concerted [HAT+SCS] mechanism. The catalytic platform was used to design a transfer of electrophilic reactivity (C–X) from one carbon to another, which we refer to as electrophilic shuttling. Thus, two nucleophiles can be used in the construction of 1,2-difunctionalization adducts from homobenzylic C–X synthons, delivering bisazole architectures and demonstrating compatibility with other nucleophile classes. A suite of transformations is developed that departs from conventional synthetic logic, for which alkyl C–X scaffolds are confined to single-site substitutions, now transforming them into nonintuitive precursors for building vicinal complexity.
Article Details
Journal Info
Science
American Association for the Advancement of Science
Authors (12)
Yufei Zhang
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.
Tamal Das
Department of Chemistry, Binghamton University, Binghamton, NY, USA.
Zi Xuan
Department of Chemistry, Worcester Polytechnic Institute, Worcester, MA, USA.
Mrinmoy Das
Department of Chemistry, Worcester Polytechnic Institute, Worcester, MA, USA.
Hammed O. Bisiriyu
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.
Alon Nudler
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.
Ben D. Parasch
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.
Matthew D. Resmini
Aubrey E. Graham
Department of Chemistry, Worcester Polytechnic Institute, Worcester, MA, USA.
David F. Watson
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.
Jennifer S. Hirschi
Department of Chemistry, Binghamton University, Binghamton, NY, USA.
Patricia Z. Musacchio
Department of Chemistry, Natural Sciences Complex, University at Buffalo, The State University of New York, Buffalo, NY, USA.