A One-Pot Diastereoselective Self Assembly of C‑Stereogenic Copper(I) Diphosphine Clusters

C-chirogenic
diphosphine-based clusters with 8-membered “chairlike”
Cu4Cl4L2 and 12-membered “drumlike”
Cu6Cl6L3 (L = diphosphine) frameworks
were prepared in one-pot syntheses from chiral diphosphines, which
were generated in situ via the double hydrophosphination reaction
in excellent enantio- and diastereoselectivity. Excellent control
over the final molecular architecture of the cluster (drum vs chair)
could be achieved by the judicious selection of the source of the
copper atoms employed in the synthetic protocol. Each cluster was
characterized by single-crystal X-ray crystallography, 1H, 13C, and 31P­{1H} NMR spectroscopy.
The synthesized clusters were found to exhibit catalytic activity
in the hydroboration reaction of α,β-unsaturated enones
with excellent yields albeit with low enantioselectivity.