124292-34-8Relevant academic research and scientific papers
Catalyst-controlled reverse selectivity in C-C bond formation: NHC-Cu-catalyzed α-selective allylic alkylation with organolithium reagents
Pizzolato, Stefano F.,Giannerini, Massimo,Bos, Pieter H.,Fa?anás-Mastral, Martín,Feringa, Ben L.
, p. 8142 - 8145 (2015)
An efficient and highly α-selective copper-catalyzed allylic alkylation of allylic halides with organolithium reagents is presented. The use of N-heterocyclic carbenes as ligands is key to reverse the common γ-selectivity of this transformation and gives rise to the corresponding linear products with high levels of regioselectivity.
Novel nickel-catalyzed coupling reaction of allyl ethers with chlorosilanes, alkyl tosylates, or alkyl halides promoted by vinyl-Grignard reagent leading to allylsilanes or alkenes
Terao, Jun,Watabe, Hiroyasu,Watanabe, Hiroyuki,Kambe, Nobuaki
, p. 1674 - 1678 (2007/10/03)
A new method for a carbon-silicon or carbon-carbon bond forming reaction between allyl ethers and chlorosilanes, alkyl tosylates, or alkyl halides giving rise to allylsilanes or alkenes has been developed. This reaction proceeds efficiently at ambient temperature by the combined use of nickel catalysts and a vinyl-Grignard reagent. A possible reaction pathway involving the formation of allyl-Grignard reagents via transmetallation of π-allylnickel complexes with the vinyl-Grignard reagent and subsequent trapping of the thus formed allyl-Grignard reagents with electrophiles is proposed.
Reaction of Phenyl-substituted Allyl-lithiums with Secondary Alkyl Halides. A Polar Process versus Single-electron Transfer
Tanaka, Jiro,Morishita, Hiroaki,Nojima, Masatomo,Kusabayashi, Shigekazu
, p. 1009 - 1014 (2007/10/02)
The reaction of 1-phenylallyl-lithium (1a) with optically active 2-halobutanes in ether in the presence of tetramethylethylenediamine or hexamethylphosphoramide gives exclusively 4-methyl-3-phenylhex-1-ene (5a) (coupling at the phenyl-substituted site) with essentially 100percent inversion of configuration.In contrast, treatment of 1,1-diphenylallyl-lithium (1b) with (-)-2-halobutanes under the same conditions results in the formation of a mixture of 4-methyl-3,3-diphenylhex-1-ene (5b) (coupling at C-1) and 4-methyl-1,1-diphenylhex-1-ene (6b) (coupling) at C-3).Moreover, C-C bond formation at the 1-position to provide (5b) is also found to proceed with complete inversionof configuration, while a small but significant loss of stereochemical integrity is observed in the case of the C-3 attack product (6b).These results suggest that a polar pathway should predominate for the formation of the C-1 attack products (5a,b), while competition between polar and single-electron-transfer processes occurs for the formation of the C-3 attack product (6b).
