Ga+-catalyzed hydrosilylation? about the surprising system Ga+/HSiR3/olefin, proof of oxidation with subvalent Ga+and silylium catalysis with perfluoroalkoxyaluminate anions
Already 1 mol% of subvalent [Ga(PhF)2]+[pf]- ([pf]- = [Al(ORF)4]-, RF = C(CF3)3) initiates the hydrosilylation of olefinic double bonds under mild conditions. Reactions with HSiMe3 and HSiEt3 as substrates efficiently yield anti-Markovnikov and anti-addit
Barthélemy, Antoine,Glootz, Kim,Hanske, Annaleah,Krossing, Ingo,Scherer, Harald
p. 439 - 453
(2022/01/22)
Synthesis of (E)-alkenes via hydroindation of C{triple bond, long}C in InCl3-NaBH4 system
In InCl3-NaBH4-MeCN system, terminal aryl alkynes could couple with aryl iodides and bromides to give disubstituted alkenes via hydroindation of C{triple bond, long}C. In the similar way, (E)-alkenylsilanes were synthesized via reduction of alkynylsilanes in tetrahydrofuran (THF) in high yields. The processes showed high regio- and stereoselectivity.
REGIOCONTROLLED SYNTHESIS OF ALLYLSILANES BY MEANS OF RHODIUM(I) OR IRIDIUM(I) CATALYZED ISOMERIZATION OF OLEFINS
Rhodium(I) or iridium(I) catalyzed migration of double-bond has been successfully applied to the regiocontrolled synthesis of allylsilane from olefin silylated at a remote sp3 carbon.