Oxidative C–N Bond Cleavage of Cyclic Amines with Ammonium Hypochlorite

Abstract

An oxidative C–N bond cleavage of cyclic amines has been developed under metal-free conditions, providing N-Cl-ω-amino acids in moderate to excellent yields. The reactions successfully proceed by using tetramethylammonium hypochlorite (TMAOCl) as an oxidant even on a gram scale. The Hofmann–Löffler–Freytag-type reaction of N-Cl-ω-amino acids to form cyclic amino acids are also demonstrated.

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

“…In addition, TMAOCl is a unique hypohalite salt requiring no additional phase-transfer reagents. Recently, we disclosed the ring-opening chlorination of N-protected cyclic amines with the use of TMAOCl as an oxidant (Scheme 3) [37]. Herein, we describe the metal-free C(sp 3 )−C(sp 3 ) bond cleavage of tert-cycloalkanols for the synthesis of ω-chloroalkyl aryl ketones with TMAOCl (Scheme 4).…”