24547-50-0Relevant academic research and scientific papers
Potassium Base-Catalyzed Michael Additions of Allylic Alcohols to α,β-Unsaturated Amides: Scope and Mechanistic Insights
Kurouchi, Hiroaki,Sai, Masahiro
supporting information, p. 3585 - 3591 (2021/06/27)
We report herein the first KHMDS-catalyzed Michael additions of allylic alcohols to α,β-unsaturated amides through allylic isomerization. The reaction proceeds smoothly in the presence of only 5 mol% of KHMDS to afford a variety of 1,5-ketoamides in high yields. Mechanistic investigations, including experimental and computational studies, reveal that the KHMDS-catalyzed in-situ generation of the enolate from the allylic alcohol through a tunneling-assisted 1,2-hydride shift is the key to the success of this transformation. (Figure presented.).
Cu-catalyzed sequential dehydrogenation-conjugate addition for β-functionalization of saturated ketones: Scope and mechanism
Jie, Xiaoming,Shang, Yaping,Zhang, Xiaofeng,Su, Weiping
supporting information, p. 5623 - 5633 (2016/05/24)
The first copper-catalyzed direct β-functionalization of saturated ketones is reported. This protocol enables diverse ketones to couple with a wide range of nitrogen, oxygen and carbon nucleophiles in generally good yields under operationally simple conditions. The detailed mechanistic studies including kinetic studies, KIE measurements, identification of reaction intermediates, EPR and UV-visible experiments were conducted, which reveal that this reaction proceeds via a novel radical-based dehydrogenation to enone and subsequent conjugate addition sequence.
