酰氯的膦硼化反应。

The phosphinoboration of acyl chlorides.

作者信息

Murphy Maia C, Trofimova Alina, LaFortune James H W, Vogels Christopher M, Geier Stephen J, Binder Justin F, Macdonald Charles L B, Stephan Douglas W, Westcott Stephen A

机构信息

Department of Chemistry and Biochemistry, Mount Allison University, Sackville, NB E4L 1G8, Canada.

Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6, Canada.

出版信息

Dalton Trans. 2020 Apr 28;49(16):5092-5099. doi: 10.1039/d0dt00579g.

DOI:10.1039/d0dt00579g

PMID:32167110

Abstract

This investigation examines the reactivity of phosphinoboronate esters Ph2PBpin (pin = 1,2-O2C2Me4) and Ph2PBcat (cat = 1,2-O2C6H4), as well as other phosphinoboron species, with various aryl and aliphatic acyl chlorides. These reactions proceed smoothly to give acyl phosphines of the type RC(O)PR'2 along with loss of a boron-chloride compound. In some cases, a second equivalent of the phosphinoboron species can add to the C[double bond, length as m-dash]O double bond at elevated temperatures to give the corresponding diphosphines RC(OBR''2)(PR'2)2. These ambiphilic diphosphines behave like substituted (1,1-bis(diphenylphosphino)methane) derivatives in a reaction of PhC(OBpin)(PPh2)2 (2a) with (η5-C9H7)Rh(η2-coe)2 (coe = cis-cyclooctene) affording the indenyl rhodium complex (η5-C9H7)Rh(PhC(OBpin)(PPh2)2) (3a) where the phosphines are bound to the metal centre in a κ2-P,P bidentate manner.

摘要

本研究考察了膦硼酸酯Ph2PBpin（pin = 1,2 - O2C2Me4）和Ph2PBcat（cat = 1,2 - O2C6H4）以及其他膦硼物种与各种芳基和脂肪族酰氯的反应活性。这些反应顺利进行，生成RC(O)PR'2型的酰基膦，同时生成一种硼氯化合物。在某些情况下，在高温下，第二当量的膦硼物种可加成到C=O双键上，生成相应的二膦RC(OBR''2)(PR'2)2。在PhC(OBpin)(PPh2)2（2a）与(η5 - C9H7)Rh(η2 - coe)2（coe = 顺式环辛烯）反应生成茚基铑配合物(η5 - C9H7)Rh(PhC(OBpin)(PPh2)2)（3a）的反应中，这些双亲性二膦的行为类似于取代的（1,1 - 双（二苯基膦基）甲烷）衍生物，其中膦以κ2 - P,P双齿方式与金属中心结合。