亲电末端次膦基金属(0)配合物与烯丙基卤化物的竞争反应还是连续反应？[2+1]环加成与碳-卤键插入反应

Competitive or sequential reaction of an electrophilic terminal phosphinidene metal(0) complex with allyl halides? [2+1]-cycloaddition vs. C-X bond insertion.

作者信息

Khan Arif Ali, Junker Philip, Schnakenburg Gregor, Espinosa Ferao Arturo, Streubel Rainer

机构信息

University School of Basic and Applied Sciences, Guru Gobind Singh Indraprastha University, Dwarka, Sec.16-C, New Delhi - 110078, India.

Institut für Anorganische Chemie, der Rheinischen Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany.

出版信息

Chem Commun (Camb). 2019 Aug 28;55(67):9987-9990. doi: 10.1039/c9cc05328j. Epub 2019 Aug 1.

DOI:10.1039/c9cc05328j

PMID:31368464

Abstract

The transiently generated electrophilic terminal phosphinidene complex [(CO)WPCH(SiMe)] reacted with allyl halides (X = F, Cl, Br) in toluene resulting in the formation of stable C-X insertion products 3a-c and diastereomeric phosphirane complexes 4a,a',b,b' as well as methylenephosphirane complex 5 as observed by P{H} NMR spectroscopy. DFT calculations revealed that a novel rearrangement of transient phosphirane complexes is responsible involving C → P X atom transfer.

摘要

瞬态生成的亲电末端磷烯配合物[(CO)WPCH(SiMe)]与烯丙基卤化物(X = F、Cl、Br)在甲苯中反应，通过磷的{1H}核磁共振光谱观察到，生成了稳定的C-X插入产物3a-c、非对映异构的磷杂环丙烷配合物4a、a'、b、b'以及亚甲基磷杂环丙烷配合物5。密度泛函理论计算表明，瞬态磷杂环丙烷配合物发生了一种涉及C→P X原子转移的新型重排反应。