57221-95-1Relevant academic research and scientific papers
Novel Copper Complexes of Chiral Diphosphines: Preparation, Structure, and Use To Form Rhodium Complex Catalysts for Chiral Hydrogenations
Townsend, John M.,Blount, John F.,Sun, Ruen Chu,Zawoiski, Sonja,Valentine, Donald
, p. 2995 - 2999 (1980)
Treatment of chiral diphosphines 5a-c and 13 ("DIOP", aryl derivatives and related substances) with CuCl in boiling ethanol gave complexes having the composition n, 6a-c and 11.Crystallizations of 6a-c from crude 70-80percent pure 5a-c and decomposition of the complexes by ammonia gave the pure diphosphines.Ligand exchange between 6a-c and 2 in methanol at 23 deg C was rapid and complete.Treatment of the resulting solutions with H2 gave active catalysts for asymmetric hydrogenations.
Rhodium-Catalyzed Enantioselective Radical Addition of CX4 Reagents to Olefins
Chen, Bo,Fang, Cheng,Liu, Peng,Ready, Joseph M.
supporting information, p. 8780 - 8784 (2017/07/17)
We describe the synthetically useful enantioselective addition of Br?CX3 (X=Cl or Br) to terminal olefins to introduce a trihalomethyl group and generate optically active secondary bromides. Computational and experimental evidence supports an asymmetric atom-transfer radical addition (ATRA) mechanism in which the stereodetermining step involves outer-sphere bromine abstraction from a [(bisphosphine)RhIIBrCl] complex by a benzylic radical intermediate. This mechanism appears unprecedented in asymmetric catalysis.
