Experimental transition state for the Corey-Bakshi-Shibata reduction

Asymmetric reductions of prochiral ketones are important transformations in the syntheses of natural products, pharmaceuticals, and fine chemicals. The Corey-Bakshi-Shibata reduction is unique among hydride transfer reductions in its tremendous substrate range and catalytic nature. Here, a coordinated computational and experimental approach is taken toward understanding the origins of the high selectivity and broad substrate range, which are hallmarks of this reduction.