17873-10-8Relevant articles and documents
Heterobimetallic s-block hydrides by σ-bond metathesis
Liptrot, David J.,Hill, Michael S.,Mahon, Mary F.
, p. 9871 - 9874 (2014)
Reactions between PhSiH3 and alkali-metal diamidoalkylmagnesiates ([M{N(SiMe3)2}2MgBu], M=Li, Na, K) provide either selective alkyl metathesis or the formation of polyhydride aggregates contingent upon the identity of the Group 1 metal. In the case of [M{N(SiMe3)2}2MgBu], this reactivity results in a structurally unprecedented dodecametallic decahydride cluster species.
Iron-copper cooperative catalysis in the reactions of alkyl grignard reagents: Exchange reaction with alkenes and carbometalation of alkynes
Shirakawa, Eiji,Ikeda, Daiji,Masui, Seiji,Yoshida, Masatoshi,Hayashi, Tamio
supporting information; experimental part, p. 272 - 279 (2012/03/07)
Iron-copper cooperative catalysis is shown to be effective for an alkene-Grignard exchange reaction and alkylmagnesiation of alkynes. The Grignard exchange between terminal alkenes (RCH=CH2) and cyclopentylmagnesium bromide was catalyzed by FeCl3 (2.5 mol %) and CuBr (5 mol %) in combination with PBu3 (10 mol %) to give RCH2CH 2MgBr in high yields. 1-Alkyl Grignard reagents add to alkynes in the presence of a catalyst system consisting of Fe(acac)3, CuBr, PBu3, and N,N,N″,N″-tetramethylethylenediamine to give β-alkylvinyl Grignard reagents. The exchange reaction and carbometalation take place on iron, whereas copper assists with the exchange of organic groups between organoiron and organomagnesium species through transmetalation with these species. Sequential reactions consisting of the alkene-Grignard exchange and the alkylmagnesiation of alkynes were successfully conducted by adding an alkyne to a mixture of the first reaction. Isomerization of Grignard reagents from 2-alkyl to 1-alkyl catalyzed by Fe-Cu also is applicable as the first 1-alkyl Grignard formation step.
