Nickel-Catalyzed Asymmetric Transfer Hydrogenation and α-Selective Deuteration of N-Sulfonyl Imines with Alcohols: Access to α-Deuterated Chiral Amines
A nickel-catalyzed enantioselective transfer hydrogenation and deuteration of N-sulfonyl imines was developed. Excellent α-selectivity and high deuterium content were achieved by using inexpensive 2-propanol-d8 as a deuterium source. As a highlight, no deuteration of β-C-H and the remote C-H of N-sulfonyl amines occurred, which is hard to achieve using other imines or by hydrogen isotope exchange with D2O. Mechanism studies indicated a stepwise pathway through the [Ni-D] intermediate.
Yang, Peng,Zhang, Li,Fu, Kaiyue,Sun, Yaxin,Wang, Xiuhua,Yue, Jieyu,Ma, Yu,Tang, Bo
Asymmetric Stepwise Reductive Amination of Sulfonamides, Sulfamates, and a Phosphinamide by Nickel Catalysis
Asymmetric reductive amination of poorly nucleophilic sulfonamides was realized in the presence of nickel catalysts and titanium alkoxide. A wide range of ketones, including enolizable ketones and some biaryl ones, were converted into sulfonamides in excellent enantiomeric excess. The cyclization of sulfamates and intermolecular reductive amination of a diarylphosphinamide were also successful. Formic acid was used as a safe and economic surrogate of high-pressure hydrogen gas.
Zhao, Xiaohu,Xu, Haiyan,Huang, Xiaolei,Zhou, Jianrong Steve
supporting information
p. 292 - 296
(2018/12/13)
SYNTHESIS OF THE RACEMIC FORM OF (Z)-1,17-DIAMINOOCTADEC-9-ENE, AN ALIPHATIC DIAMINE FROM COCCINELLIDAE. DETERMINATION OF THE ABSOLUTE CONFIGURATION OF THE (+)-NATURALLY-OCCURRING ANTIPODE
The total synthesis of the title compound (1) has been achieved.Also reported is the use of lanthanide induced shifts in 1H NMR spectroscopy to assign the absolute configuration of the α-carbon atom in chiral primary α-methylalkylamines.Application of this empirical method to natural (+)-1 shows that it has the R-configuration at C-17.
Braconnier, M.F.,Braekman, J.C.,Daloze, D.
p. 605 - 614
(2007/10/02)
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