Abstract
Abstract Utilizing 2,4,6-tri-tert-butylphenyl as a sterically demanding group (abbreviated as Mes*), we have been successful in isolation, characterization, physical and chemical property investigation of low-coordinate organophosphorus compounds such as those carrying P=P and P=C bonds. Diphosphene, 1-phosphaethene, 1,3-diphosphaallene, 1-phosphaallene, and 3,4-diphosphinidenecyclobutenes are discussed in terms of stereochemistry including E/Z isomerization around P=P or P=C bond and R/S resolution of rotational isomers around crowded P–C bonds with chiral HPLC column. (π-Allyl)palladium complexes ligated with 3,4-diphosphinidenecyclobutene are useful in such catalytic organic reactions as the Tsuji-Trost reaction by which from a chiral s-alcohol, the corresponding chiral amine is obtained with retention of chirality suggesting double inversion process.
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