Wilson Daniel W N, Mehta Meera, Franco Mauricio P, McGrady John E, Goicoechea Jose M
Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Department of Chemistry, University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Chemistry. 2020 Oct 21;26(59):13462-13467. doi: 10.1002/chem.202002226. Epub 2020 Oct 8.
We describe the reactivity of two linkage isomers of a boryl-phosphaethynolate, [B]OCP and [B]PCO (where [B]=N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl), towards tris- (pentafluorophenyl)borane (BCF). These reactions afforded three constitutional isomers all of which contain a phosphaalkene core. [B]OCP reacts with BCF through a 1,2 carboboration reaction to afford a novel phosphaalkene, E-[B]O{(C F ) B}C=P(C F ), which subsequently undergoes a rearrangement process involving migration of both the boryloxy and pentafluorophenyl substituents to afford Z-{(C F ) B}(C F )C=PO[B]. By contrast, [B]PCO undergoes a 1,3-carboboration process accompanied by migration of the N,N'-bis(2,6-diisopropylphenyl)-2,3-dihydro-1H-1,3,2-diazaboryl to the carbon centre.
我们描述了硼基磷乙炔醇盐的两种键合异构体[B]OCP和[B]PCO（其中[B]=N，N'-双（2,6-二异丙基苯基）-2,3-二氢-1H-1,3,2-二氮杂硼基）与三（五氟苯基）硼烷（BCF）的反应活性。这些反应产生了三种构造异构体，它们都含有一个磷烯核心。[B]OCP通过1,2-碳硼化反应与BCF反应，生成一种新型磷烯E-[B]O{(CF)B}C=P(CF)，随后该磷烯经历一个重排过程，涉及硼氧基和五氟苯基取代基的迁移，生成Z-{(CF)B}(CF)C=PO[B]。相比之下，[B]PCO经历1,3-碳硼化过程，同时N，N'-双（2,6-二异丙基苯基）-2,3-二氢-1H-1,3,2-二氮杂硼基迁移到碳中心。
