Synthesis of Chiral a-(iV-Sulfoxiinido) Phosphines, Phosphine Oxides, and Phosphonates through Hydrophosphination and Hydrophosphorylation of N-Vinyl Sulfoximines

摘要

The reaction of TV-vinyl sulfoximines with HPPh_2, HP(O)Ph_2, and HP(O)(OMe)_2 gave the corresponding a-(N-sulfox-imido) phosphines, phosphine oxides, and phosphonates, respectively, with high regioselectivity in high yield. The N-vinyl sulfoximines showed an enamine-like regioselectivity in hydrophosphination and hydrophosphorylation (Pudovik reaction). While the acid-catalyzed hydrolysis of a cyclic N-vinyl siilfoximine gave the corresponding NH-sulfoximine and cyclohexanone, its hydro-boration/oxidation afforded the corresponding N-(beta-hydroxycyclo-hexenyl) sulfoximine. The structure of an a-(N-sulfoximido) phosphine was determined by X-ray crystal structure analysis.