Metal‐Free Geminal Difunctionalization of Diazocarbonyl Compounds: A One‐Pot Multicomponent Strategy for the Construction of α,β‐Diamino Carbonyl Derivatives

Abstract

An unprecedented three-component domino oxidative coupling of diazocompounds for the efficient synthesis of α-azido-β-amino esters with non-activated dimethylamino compounds and simple TMSN was achieved. The main features of this method include metal-free catalysis, satisfactory functional group tolerance, general applicability in complex molecule architectures, and excellent diastereoselectivity in the presence of chiral auxiliaries. In addition, several related control experiments have been conducted to investigate the reaction mechanism.

Three‐Component Reaction for the Synthesis of Highly Functionalized Propargyl Ethers

“…In the absence of a metal‐catalyst, Murphy and co‐workers have first reported dihalogenation reactions . More recent examples involve acetoxyaminoalkylation and azidoaminoalkylation . The first transformations involving metal carbene intermediates were reported independently by our group and Szabo and co‐workers .…”

Recent Progress in the Construction of C−N Bonds via Metal‐Free Radical C(sp3)−H Functionalization

“…Shi and co‐workers developed a method for the synthesis of α‐azido‐β‐amino esters with non‐activated dimethylamines and simple TMSN 3 via domino oxidative coupling in 2018 (Scheme ) . MeCN was used as the solvent and BI‐OH was used as the oxidant.…”

Reactions between Diazo Compounds and Hypervalent Iodine(III) Reagents

“…In 2018, Shi and co‐workers developed a geminal difunctionalization of α‐diazo carbonyl compounds 77 to construct α‐azido‐β‐amino carbonyl derivatives 80 (Scheme ) . Based on preliminary mechanistic studies, the cyclic hydroxybenziodoxole (BI‐OH) 81 was proposed to initiate the radical process by generating the azide radical and α‐aminoalkyl radical AIV successively.…”