Versatile Dehydrogenative Alcohol Silylation Catalyzed by Cu(I)—Phosphine Complex.

Abstract

Silylation O 0278Versatile Dehydrogenative Alcohol Silylation Catalyzed by Cu(I)-Phosphine Complex.-The complexes of xanthene-based diphosphines (I) with CuO-tBu are highly efficient catalysts for dehydrogenative alcohol silylation. They provide an unprecedented broad substrate scope and a high level of chemoselectivity. The selective silylation of (IIb) versus (IIc) is also investigated. -(ITO*, H.; WATANABE, A.; SAWAMURA, M.; Org. Lett. 7 (2005) 9, 1869-1871; Div. Chem., Grad. Sch. Sci., Hokkaido Univ., Sapporo 060, Japan; Eng.) -Y. Steudel 38-064

Copper polyhydrides: A powerful tool in chemical synthesis. Stryker’s reagent in perspective

“…In this case, the ligand can be an asymmetric phosphine, which offers the possibility of directing the reduction reaction along a path leading to enantiomeric excess. As an example of this strategy, we can cite work on the atropoenantioselective reduction of lactones [81] , asymmetric hydroxylation of vinylarenes and vinyl heterocycles [82] , diastereo-and enantioselective hydroamination of trisubstituted alkenes [83] , regio-and enantioselective hydroxymethylation of styrenes and 1,3-dienes with CO 2 [84] ,diastereo-and enantioselective preparation of 2,3-disubstituted indolines [85] , enantioselective reduction of α,β-aryl-β-boronyl α,β-unsaturated esters [86] , and dehydrogenated silylation of alcohols [87] . The possibilities of using [(Ph 3 P)CuH] 6 and its analogues in asymmetric synthesis and catalysis protocols is quite broad and as can be sensed will be the focus of research in the short, medium and long term.…”

Selective Long-Distance Isomerization of Terminal Alkenes via Nondissociative Chain Walking

“…The analytical data of 1b are in good agreement with those reported in literature. 15 Silyl Ether 1c. General Procedure A was followed with 1.41 g of 9decen-1-ol and 3.59 g of tert-butyldiphenylsilyl chloride without using DMAP.…”