2185014-88-2Relevant academic research and scientific papers
Nickel-Catalyzed Enantioselective Hydroboration of Vinylarenes
Tran, Hai N.,Stanley, Levi M.
supporting information, p. 395 - 399 (2021/12/27)
The enantioselective hydroboration of vinylarenes catalyzed by a chiral, nonracemic nickel catalyst is presented as a facile method for generating chiral benzylic boronate esters. Various vinylarenes react with bis(pinacolato)diboron (B2pin2) in the presence of MeOH as a hydride source to form chiral boronate esters in up to 92% yield with up to 94% ee. The use of anhydrous Me4NF to activate B2pin2 is crucial for ensuring fast transmetalation to achieve high enantioselectivities.
Nickel-Catalyzed Asymmetric Hydroarylation of Vinylarenes: Direct Enantioselective Synthesis of Chiral 1,1-Diarylethanes
Tran, Hai N.,Burgett, Russell W.,Stanley, Levi M.
, p. 3836 - 3849 (2021/03/01)
The enantioselective hydroarylation of vinylarenes catalyzed by a chiral, non-racemic nickel catalyst is presented as a facile method to generate chiral 1,1-diarylethanes. These reactions proceed via formation of a chiral, non-racemic nickel benzyl intermediate. Transmetalation with arylboron nucleophiles and subsequent reductive elimination enable the formation of a variety of chiral 1,1-diarylethanes. The 1,1-diarylethane products from reactions of arylboronic acids containing electron-donating substituents are formed with typically greater than 90% ee, while the 1,1-diarylethanes generated from reactions of arylboronic acids containing electron-withdrawing groups are generated with typically less than 80% ee. These results are consistent with the rate of transmetalation with an arylboron nucleophile playing a key role in the enantioselectivity of these hydroarylation reactions. This mechanistic insight has led to the development of reactions of neo-pentylglycolate esters of arylboronic acids with vinylarenes that occur with higher enantioselectivities based on increased rates of transmetalation.
Copper-Catalyzed Enantioselective Arylative Desymmetrization of Prochiral Cyclopentenes with Diaryliodonium Salts
Wu, Hua,Wang, Qian,Zhu, Jieping
supporting information, p. 2721 - 2725 (2018/02/09)
A copper-catalyzed enantioselective arylative desymmetrization of prochiral cyclopentenes with diaryliodonium salts was developed. In the presence of a catalytic amount of a chiral copper–bisoxazoline complex, which was generated in situ, the reaction of 4-substituted or 4,4-disubstituted cyclopent-1-enes with diaryliodonium hexafluoroarsenates afforded the chiral arylated products in good yields with excellent enantioselectivity. A cyclohexyl-containing Box ligand was essential for the high enantioselectivity. Transformation of the enantiomerically enriched adducts into other chiral building blocks is also documented.
