Silver(I)‐Catalyzed Hydroazidation of Ethynyl Carbinols: Synthesis of 2‐Azidoallyl Alcohols

Abstract

The hydroazidation of alkynes is the most straightforward pathway to synthetically useful vinyl azides. However, a general hydroazidation of alkynes remains elusive. Herein, a chemo-and regioselective transformation of ethynyl carbinols into vinyl azides is described. This reaction produces a wide variety of 2-azidoallyl alcohols with high efficiency and in good to excellent yields. These compounds constitute a new class of densely functionalized synthetic intermediates. Their synthetic potential has been demonstrated by further transformations into NH aziridines. The mechanistic aspects of the reaction will attract the attention of chemists working on alkyne chemistry and silver catalysis. The findings that are described in this paper represent significant advances in the regioselective hydroelementation of alkynes and open a new reaction manifold for exploitation.

Silver‐Catalyzed Stereoselective Aminosulfonylation of Alkynes

“…Meanwhile, TolSO 2 TMS ( A ) is generated from sulfinate salt 2 a (possibly promoted by Ag I ). Such intermediates are known to be somewhat unstable, and could be oxidized by Ag I to give a radical cation B , which could then release sulfonyl radical C and a trimethylsilyl cation . The latter is captured by water to produce trimethylsilanol with release of a proton, which could affect protodemetalation of intermediate A′ to give the observed vinyl azide ( VA ).…”

Bi(OTf)3‐catalyed One‐pot Synthesis of α‐Halo‐β‐amino Ketones and Acyl Aziridines from 3‐Aryl Propargyl Alcohols

“…Aziridinyl ketone is a versatile building block for it undergo various transformation to provide diverse amine derivatives [1] . Thus, a large number of methods for its synthesis have been developed, such as aziridination of vinyl ketones using SESN 3 , [2] synthesis of NH aziridines from 2‐azidoallyl alcohols, [3] direct transformation of propargylic N‐hydroxylamines to acylaziridines, [4] rearrangement of isoxazolines, [5] and aziridination of chalcones [6] or vicinal haloamines [7] . Although chemists have made great achievements in the synthesis of acyl aziridines in the past few decades, but these methods have more or less defects.…”