Iron-Catalyzed Oxyalkylation of Terminal Alkynes with Alkyl Iodides

Abstract

A general oxyalkylation of terminal alkynes enabled by iron catalysis has been developed. Primary and secondary alkyl iodides acted as the alkylating reagents and afforded a range of α-alkylated ketones under mild reaction conditions. Acetyl tert-butyl peroxide (TBPA) was used as the radical relay precursor, providing the initiated methyl radical to start the radical relay process. Preliminary mechanistic studies were conducted, and late-stage functionalizations of natural product derivatives were performed.

Synthesis of ω-Chloroalkyl Aryl Ketones via C–C Bond Cleavage of tert-Cycloalkanols with Tetramethylammonium Hypochlorite

“…Aqueous tetramethylammonium hypochlorite (TMAOCl) was prepared from aqueous tetramethylammonium hydroxide (TMAOH) by ion-exchange method (14.0 wt% TMAOCl, 7.86 wt% available chlorine, pH = 11.5) [36]. Compounds 1b [20], 1c [45], 1d-1g [20], 1h [46], 1i [47], 1j-1k [20], 1l [48], and 1m-1o [20] were synthesized according to the reported methods.…”