Regulating iminophosphorane PN bond reactivity through geometric constraints with cage-shaped triarylphosphines.

Structure-reactivity investigations and quantum-chemical parametrization of steric and electronic properties of geometrically constrained iminophosphoranes enabled the design of new frustrated Lewis pairs and revealed unusual properties at the phosphonium center embedded in the cage-shaped triptycene tricyclic scaffold.

Ruthenium-Catalyzed Reductive Coupling of Epoxides with Primary Alcohols via Hydrogen Transfer Catalysis.

Herein, we report the ruthenium-catalyzed synthesis of ß-alkylated secondary alcohols via the regioselective ring-opening of epoxides with feedstock primary alcohols. The reaction utilized alcohol as the carbon source and the terminal reductant. Kinetic and labeling experiments elucidate the hydrogen transfer catalysis that operates via tandem Markovnikov selective transfer hydrogenation of terminal epoxides and hydrogen transfer-mediated cross-coupling of the resulting alcohol with primary alcohol substrates. A broad scope (40 examples including drugs/natural product derivatives) and excellent regioselectivity for a variety of substrates were shown.