Gold(I) Complexation of the Phosphanoxy-Substituted Phosphaalkenes for the Activation-Free LAuCl Catalysis.

Gold(I) Complexation of the Phosphanoxy-Substituted Phosphaalkenes for the Activation-Free LAuCl Catalysis.
Chemistry. 2020 Oct 20;:
Authors: Kato M, Ueta Y, Ito S
Abstract
The phosphanoxy-substituted phosphaalkene bearing the P=C-O-P skeleton can be prepared from diphosphene Mes*P=PMes* (Mes* = 2,4,6- t Bu 3 C 6 H 2 ), and the use for catalysis is of interest. In this paper, complexation of the phosphanoxy-substituted phosphaalkenes with gold are investigated, and the catalytic activity of the mono- and bis(chlorogold) complexes are subsequently evaluated. Reaction of the P=C-O-P compound with (tht)AuCl (tht = tetrahydrothiophene) showed dominant coordination on the sp 3 phosphorus, and complete coordination on the sp 2 phosphorus required removal of tetrahydrothiophene. Atoms-In-Molecules (AIM) analysis based on the X-ray structure of the chlorogold complex indicated pseudo coordinating interaction between the gold centre and the P=C unit. The bis(chlorogold) complexes indicated the conformational isomerism, and catalyzed cycloisomerization/alkoxyclization of 1,6-enyne and for hydration of terminal alkyne without the activation treatment. Even the mono(chlorogold) complexes catalyzed the alkoxycyclization reaction without silver co-catalyst, indicating that the alcohols were effective for the activation of AuCl unit.
PMID: 33078876 [PubMed - as supplied by publisher]

Source: Chemistry - October 20, 2020 Category: Chemistry Authors: Kato M, Ueta Y, Ito S Tags: Chemistry Source Type: research