The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding alpha-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu* 2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of beta,beta-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.
Chiral bidentate hemi-labile bis(phosphine) monoxide ligands were shown to be quite effective in various copper-catalyzed transformations. Among them, the nucleophilic addition to imines, the conjugate addition to α,β-unsaturated nitro derivatives, and the conjugate reduction of α,β-unsaturated sulfones generally gave good to excellent yields and high enantiomeric excesses.
The structure of the title compound [alternatively called (R)-(−)-1-azabicyclo[2.2.2]octan-3-ol], C7H13NO, at 100 K has hexagonal (P61) symmetry. The structure shows a twist along the C—N pseudo-threefold axis. In the crystal, molecules are linked via O—H⋯N hydrogen bonds, forming infinite chains along the c-axis direction. The crystal studied was twinned by merohedry (twin law: 010, 100, 00-1; population: 0.925:0.075)
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