107772-10-1Relevant academic research and scientific papers
Regiocontrol in catalytic reductive couplings through alterations of silane rate dependence
Jackson, Evan P.,Montgomery, John
, p. 958 - 963 (2015/01/30)
Combinations of ligand, reducing agent, and reaction conditions have been identified that allow alteration in the rate- and regioselectivity-determining step of nickel-catalyzed aldehyde-alkyne reductive couplings. Whereas previously developed protocols involve metallacycle-forming oxidative cyclization as the rate-determining step, this study illustrates that the combination of large ligands, large silanes, and elevated reaction temperature alters the rate- and regiochemistry-determining step for one of the two possible product regioisomers. These modifications render metallacycle formation reversible for the minor isomer pathway, and σ-bond metathesis of the metallacycle Ni-O bond with the silane reductant becomes rate limiting. The ability to tune regiocontrol via this alteration in reversibility of a key step allows highly regioselective outcomes that were not possible using previously developed methods.
An efficient CuCN-catalyzed synthesis of optically active 2,3-allenols from optically active 1-substituted 4-chloro-2-butyn-1-ols
Li, Jing,Kong, Wangqing,Fu, Chunling,Ma, Shengming
supporting information; experimental part, p. 5104 - 5106 (2009/10/17)
(Chemical Equation Presented) The sequential treatment of optically active terminal propargylic alcohols with n-BuLi/(HCHO)n and regioselective chlorination afforded the corresponding optically active 4-chloro-2-butyn-1-ols. With R1
