23381-93-3Relevant academic research and scientific papers
Copper(i)-catalysed asymmetric allylic reductions with hydrosilanes
Thanh Nguyen,Thiel, Niklas O.,Teichert, Johannes F.
supporting information, p. 11686 - 11689 (2017/11/03)
A copper(i)-catalysed asymmetric allylic reduction enables a regio- and stereoselective transfer of a hydride nucleophile in an SN2′-fashion onto allylic bromides. This transformation represents a conceptually orthogonal approach to allylic substitution reactions with carbon nucleophiles. A copper(i) complex based upon a chiral N-heterocyclic carbene (NHC) ligand allows for stereoselectivity reaching 99% ee. The catalyst enables a stereoconvergent reaction irrespective of the double bond configuration of the starting materials.
Copper-Catalyzed Regioselective Hydroalkylation of 1,3-Dienes with Alkyl Fluorides and Grignard Reagents
Iwasaki, Takanori,Shimizu, Ryohei,Imanishi, Reiko,Kuniyasu, Hitoshi,Kambe, Nobuaki
, p. 9347 - 9350 (2015/08/06)
Copper complexes generated in situ from CuCl2, alkyl Grignard reagents, and 1,3-dienes play important roles as catalytic active species for the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides through C-F bond cleavage. The alkyl group is introduced to an internal carbon atom of the 1,3-diene regioselectively, thus giving rise to the branched terminal alkene product. Making the switch: A copper-hydride species, generated by the treatment of a copper salt with alkyl Grignard reagents, catalyzes the 1,2-hydroalkylation of 1,3-dienes by alkyl fluorides and Grignard reagents. The alkyl group of the alkyl fluoride is selectively introduced to an internal carbon atom of the 1,3-diene and the Grignard reagent acts as hydride source to give the branched terminal alkene, even in the presence of alkenes and alkynes.
An alternative regioselective ring-opening of epoxides to chlorohydrins mediated by chlorotitanium(IV) reagents
Nishitani, Kiyoshi,Shinyama, Kyoko,Yamakawa, Koji
, p. 191 - 197 (2008/09/17)
A regioselective cleavage of various epoxides to vic-chlorohydrin isomers by using TiCl4 or TiCl4-Ti(O-i-Pr)4 complex was investigated. The less substituted alcohols, C2-attack products, were formed by the use of TiCl4 in CH2Cl2. On the other hand, the less substituted chlorides, Cl-attack products, were formed by using TiCI(O-i-Pr)3 in DMF. These regioselectivities depend on both the acidity of the Lewis acids and the polarity of the solvents.
