27911-12-2Relevant articles and documents
Controllable, Sequential, and Stereoselective C-H Allylic Alkylation of Alkenes
Qin, Ling,Sharique, Mohammed,Tambar, Uttam K.
, p. 17305 - 17313 (2019/11/03)
The direct conversion of C-H bonds into new C-C bonds represents a powerful approach to generate complex molecules from simple starting materials. However, a general and controllable method for the sequential conversion of a methyl group into a fully substituted carbon center remains a challenge. We report a new method for the selective and sequential replacement of three C-H bonds at the allylic position of propylene and other simple terminal alkenes with different carbon groups derived from Grignard reagents. A copper catalyst and electron-rich biaryl phosphine ligand facilitate the formation of allylic alkylation products in high branch selectivity. We also present conditions for the generation of enantioenriched allylic alkylation products in the presence of catalytic copper and a chiral phosphine ligand. With this approach, diverse and complex products with substituted carbon centers can be generated from simple and abundant feedstock chemicals.
Catalytic Semireduction of Internal Alkynes with All-Metal Aromatic Complexes
Deyris, Pierre-Alexandre,Ca?eque, Tatiana,Wang, Yanlan,Retailleau, Pascal,Bigi, Franca,Maggi, Raimondo,Maestri, Giovanni,Malacria, Max
, p. 3266 - 3269 (2015/10/28)
A simple catalytic method involving all-metal aromatic frameworks as precatalysts ensures an efficient route to (Z)-alkenes. Aromatic triangular palladium clusters were used to reduce internal alkynes without any trace of the formation of alkane side products. These trinuclear complexes provide a catalytic system that parallels the activity and selectivity of their best mononuclear peers, and the catalyst likely operates through complementary mechanisms.
Mechanistic insight into copper-catalysed allylic substitutions with bis(triorganosilyl) zincs. Enantiospecific preparation of α-chiral silanes
Schmidtmann, Eric S.,Oestreich, Martin
, p. 3643 - 3645 (2008/09/20)
Isotopic desymmetrisation, as well as (stereo)chemical correlation, has illuminated significant aspects of the σ-π-σ mechanism of copper-catalysed allylic substitution reactions: an enantiospecific and regioselective access to α-chiral silanes is presente