Reactivity of a Sterically Unencumbered α‐Borylated Phosphorus Ylide towards Small Molecules
作者:Michael Radius、Ewald Sattler、Helga Berberich、Frank Breher
DOI:10.1002/chem.201902681
日期:2019.9.18
approach. The synthesis and characterization of Me3PC(H)B(iBu)2 (1), consisting of small Me substituents on phosphorous and iBu residues on boron, is reported. Compound 1 is accessible through a novel synthetic approach, which has been further elucidated through DFT studies. The reactivity of 1 towards various small molecules was probed and compared with that of a previously published derivative, Ph3PC(Me)BEt2
结合实验和量子化学方法,研究了取代基对α-硼化磷酰化物(α-BCPs)的影响。报道了Me 3 PC(H)B(i Bu)2(1)的合成和表征,该Me 3 PC(H)B(i Bu)2(1)由磷上的小Me取代基和硼上的i Bu残基组成。化合物1可通过新颖的合成方法获得,该方法已通过DFT研究进一步阐明。探索了1对各种小分子的反应性,并将其与先前发布的衍生物Ph 3 PC(Me)BEt 2(2)进行了比较。两种α-BCP均与NH反应3经历杂合NH键裂解。在1与CO和CO 2的反应产物中观察到不同的二聚和三聚环结构。用PhNCO和PHNCS分别分离出预期的插入产物[Me 3 PC(H)(PhNCO)B(i Bu)2 ]和[Me 3 PC(H)(PhNCS)B(i Bu)2 ]。