Heteroatom-directed C-H borylation of cyclopropanes and cyclobutanes was achieved with silica-supported monophosphane-Ir catalysts. Borylation occurred at the C-H bonds located γ to the directing N or O atoms with exceptional cis stereoselectivity relative to the directing groups. This protocol was applied to the borylation of a tertiary C-H bond of a ring-fused cyclopropane.

The synthesis and characterization of a novel chiral phosphine-phosphoric acid ligand, (R)-3-diphenylphosphino-1,1'-binaphthyl-2,2'-diyl hydrogenphosphate (2) and its rhodium(I) complexes are described. The single-crystal X-ray diffraction analysis of 2 showed the intermolecular hydrogen-bonding network of the phosphoric acid moiety. The reactions of 2 with [RhCl(cod)] 2 in the presence of KOtBu or with [Rh(acac)(CO) 2 ] (acac = acetylacetonate) gave P,O-chelating rhodium(I) complexes [Rh(2-H +)(cod)] 3 or [Rh(2-H +)(CO)] 2 4, respectively. Their molecular structures were determined by single-crystal X-ray diffraction.

A silica‐supported caged trialkylphosphane is applied as efficient heterogeneous ligand in the Ir‐catalyzed N‐ or O‐atom directed C—H borylation of cyclopropanes and a few cyclobutanes to give cis‐products.