Involvement of Intramolecular Hydride Transfer in the Formation of Alkanes from Palladium Alkyls
摘要:
Intramolecular hydride transfer in a dimer between Pd atoms and reductiue elimination of H and a benzyl moiety to give PhCH2CH2C6F5 (3) is the main decomposition pathway for the hydrido species generated from the eta(3)-benzyEpalladium derivative [Pd-2(mu-Br)(2)(eta(3)-CHPhCH2C6F5)(2)] (1). The commonly accepted decomposition of the palladium hydride to give Pd(0) and HX, followed by acid attack on 1 to produce the alkane, is ruled out in this case.
“Gated Migration” for Enantioselective Synthesis of Palladium Allyls Using a “PdHBr” Synthon
作者:Ana C. Albéniz、Pablo Espinet、Yong-Shou Lin、Blanca Martín-Ruiz
DOI:10.1021/om990267a
日期:1999.8.1
palladium cyclic allyl complexes is accomplished by reaction of “PdHBr” with several chiral cyclic terpenes. The strategy used involves a 100% stereoselective Pd-migration from an attached chain to the ring through a chiral carbon (“gated migration”). “PdHBr” species are produced by β-H elimination in the benzylic moiety of [Pd2(μ-Br)2(η3-PfCH2CHPh)2] (1, Pf = C6F5). The allylic complexes prepared are transformed