Metal-Free Z-Selective Allylic C-H Nitrogenation, Oxygenation, and Carbonation of Alkenes by Thianthrenation

05 November 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Selective functionalization of allylic C-H bonds into other chemical bonds with Z-selectivity are among the most straightforward and attractive, yet challenging transformations. Herein, a transition-metal-free protocol for direct allylic C-H nitrogenation, oxygenation, and carbonation of alkenes by thianthrenation was developed. This operationally simple protocol allows for the unified allylic C-H amination, esterification, etherification, and arylation of vinyl thiathrenium salts. Notably, the reaction preferably provides multialkyl substituted allylic amines, esters, and ethers with Z-selectivity. The reaction proceeds under mild conditions with excellent functional group tolerance and could be applied to late-stage allylation of natural products, drug molecules and peptides with excellent chemoselectivity.


metal-free C-H functionalizations
thianthrenium salt
allylic esterification
allylic C-H functionalizations
allylic amination

Supplementary materials

Supporting Infomarion
This file includes: Optimization of Reaction Conditions Substrate Synthesis and Characterization General Procedure for the Allylic C-H Functionalizations Gram-Scale Synthesis Characterization of Allylic C-H Functionalization Products Mechanistic Study Crystallographic Data NMR Spectra of New Compounds


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