Alkylidenephosphines

Niecke, Edgar; Ruban, Alexander V.; Raab, M.

doi:10.1002/chin.200532240

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“…As described above, developing catalytically active mononuclear phosphaethene‐chloro‐gold complexes would be desirable for analyzing the mechanisms of unique gold catalysis. After establishing the KTC process for 1 , we investigated the catalytic activity of chloro‐gold complexes bearing ligated 2,2‐diaryl‐1‐phosphaethenes [Mes*P=C(Ar 1 )Ar 2 ; Mes* = 2,4,6‐tri‐ tert ‐butylphenyl], which were synthesized through sequential catalytic arylation reactions from 1 (see the Supporting Information) , …”

Section: Introductionmentioning

confidence: 99%

Stereoselective Catalytic Synthesis of Alkynylated Phosphaethenes Leading to Activation‐Free Gold Catalysis

2017

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The π‐accepting property of alkene‐like phosphaethenes (–P=C<) is attractive for the development of Lewis acidic transition‐metal catalysts. The stereoselective monoalkynylation of a sterically encumbered gem‐dibromophosphaethene by a Sonogashira process has been accomplished, and the corresponding 2‐alkynyl‐2‐bromo‐1‐phosphaethenes were obtained. Subsequent arylation of the 2‐alkynyl‐2‐bromo‐1‐phosphaethenes by the palladium version of the Kumada–Tamao–Corriu (KTC) reaction gave the corresponding 2‐alkynyl‐2‐aryl‐1‐phosphaethenes through an inversion of the configuration. The 2‐alkynyl‐2‐aryl‐1‐phosphaethenes were converted into the corresponding chloro‐gold(I) complexes, and screening of their catalytic activity revealed that both appropriate π‐conjugative substituents and the stereochemistry were decisive for the efficiency of the gold‐catalyzed reactions under activation‐free conditions. Chloro‐gold complexes bearing 2,2‐diaryl‐1‐phosphaethene ligands showed moderate‐to‐good catalytic activity.

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Section: Introductionmentioning

confidence: 99%