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Reactivity of a Sterically Unencumbered α-Borylated Phosphorus Ylide towards Small Molecules.

ABSTRACT: The influence of substituents on α-borylated phosphorus ylides (α-BCPs) has been investigated in a combined experimental and quantum chemical approach. The synthesis and characterization of Me3 PC(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, Ph3 PC(Me)BEt2 (2). Both α-BCPs react with NH3 to undergo heterolytic N-H bond cleavage. Different di- and trimeric ring structures were observed in the reaction products of 1 with CO and CO2 . With PhNCO and PHNCS, the expected insertion products [Me3 PC(H)(PhNCO)B(iBu)2 ] and [Me3 PC(H)(PhNCS)B(iBu)2 ], respectively, were isolated.

SUBMITTER: Radius M

PROVIDER: S-EPMC6771871 | biostudies-other | 2019 Sep

REPOSITORIES: biostudies-other

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Reactivity of a Sterically Unencumbered α-Borylated Phosphorus Ylide towards Small Molecules.

Radius Michael M Sattler Ewald E Berberich Helga H Breher Frank F

Chemistry (Weinheim an der Bergstrasse, Germany) 20190823 52

The influence of substituents on α-borylated phosphorus ylides (α-BCPs) has been investigated in a combined experimental and quantum chemical approach. The synthesis and characterization of Me<sub>3</sub> PC(H)B(iBu)<sub>2</sub> (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 pro ...[more]

PMID: 31355482

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