联烯型和烯型迈克尔受体对膦的反应活性。

Reactivities of allenic and olefinic Michael acceptors towards phosphines.

作者信息

An Feng, Jangra Harish, Wei Yin, Shi Min, Zipse Hendrik, Ofial Armin R

机构信息

Department Chemie, Ludwig-Maximilians-Universtität München, Butenandtstr. 5-13, München 81377, Germany.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. China.

出版信息

Chem Commun (Camb). 2022 Mar 8;58(20):3358-3361. doi: 10.1039/d1cc06786a.

DOI:10.1039/d1cc06786a

PMID:35188503

Abstract

The kinetics of the reactions of tributylphosphine with allenic and olefinic Michael acceptors in dichloromethane at 20 °C was followed by photometric and NMR spectroscopic methods. Combination with DFT-calculated methyl anion affinities revealed the relevance of retroaddition barriers in phosphine-catalysed reactions when mixtures of allenic and olefinic substrates are used.

摘要

在20℃下，采用光度法和核磁共振光谱法跟踪三丁基膦与丙二烯型和烯烃型迈克尔受体在二氯甲烷中的反应动力学。结合密度泛函理论（DFT）计算的甲基负离子亲和力表明，当使用丙二烯型和烯烃型底物的混合物时，逆加成势垒在膦催化反应中具有重要意义。