81256-50-0Relevant articles and documents
Reversing the role of the metal - oxygen π-bond. Chemoselective catalytic reductions with a rhenium(V)-dioxo complex
Kennedy-Smith, Joshua J.,Nolin, Kristine A.,Gunterman, Haluna P.,Toste, F.Dean
, p. 4056 - 4057 (2003)
The metal-oxygen bond plays a critical role in some of the most important biological and synthetic reactions. However, the majority of these processes result in the oxidation of the target organic substrate; applications of this class of metal complexes to other organic transformations are extremely rare. In this paper, we report a new type of catalytic process in which complexes with metal-oxygen multiple bonds are used as reductants rather than oxidants. The overall reaction provides a highly chemoselective reduction/protection of carbonyl groups. In addition to providing a new way of catalyzing organic reactions, these catalysts can be used in the presence of a wide range of other functional groups such as amino, cyano, nitro, aryl halo, ester, and alkene; unlike many of their late metal relatives, they are inexpensive as well as air and moisture tolerant. Copyright
Intramolecular Hydrogen Transfer Reactions of o-(Bromophenyl)dialkylsilyl Ethers. Preparation of Rapamycin-d1
Curran, Dennis P.,Somayajula, Kasi V.,Yu, Hosung
, p. 2295 - 2298 (2007/10/02)
Radical translocations of o-(bromophenyl)dimethylsilyl ethers are efficient, but yields of α-silyloxy alkyl radicals formed by 1,5-hydrogen transfer are limited to 65-90 percent by competing 1,6- and 1,7-hydrogen transfers.Similarities in substituent effects on 1,5-hydrogen transfers and radical cyclizations are identified.
