α,α,α-Trifluoroacetophenone (2), which is susceptible to noncatalytic reduction by BH3, could be reduced to chiral alcohol up to 90% ee by using electronically tuned-CBS catalyst (1) with BH3. The enantioselectivities highly correlated with the differential orbital energies between 1–BH3 adduct and 2, which were calculated by DFT method.

The reductive elimination of biphenyl from cis-[Pt(Ph)2(diphosphine)] (3) was studied to clarify the electronic effects of diphosphine ligands on the reaction. Reaction kinetic data were evaluated in d8-toluene within 80−110 °C using 1,2-bis(diphenylphosphino)ethane (dppe) and seven of its fluoroaromatic analogues as ancillary diphosphine ligands. The fastest reaction rate corresponded to 3, bearing the electron-poor 1,2-bis[bis(pentafluorophenyl)phosphino]ethane (dfppe) ligand, and was 1240 times faster than that for dppe-bearing 3, which has the slowest. The estimated rate constants k were highly correlated with Taft’s σ* values for phosphorus-bound aromatics in 3. However, their correlation was split between 2,6-fluorine aromatic and 2,6-hydrogen aromatic-bearing diphosphines, suggesting steric effects from the 2,6-fluorine atoms. The observed ΔH⧧ values were correlated with theoretical values, which were calculated by the DFT method. The correlations revealed that electron-poor diphosphine ligands decrease the energy gaps between the HOMO−1 of 3 and the HOMO of transition state 3-TS, including the platinum d orbital, and reduce the destabilization of the platinum d orbital upon binding with the diphosphine in 3-TS as compared to the cases of an electron-donating ligand. This last mentioned effect is the true nature of electronic influence of the electron-poor diphosphine ligands in the reductive elimination from 3.

Electron-poor chiral diphosphine ligands, MeO-F28-BIPHEP (1a) and MeO-F12-BIPHEP (1b), were synthesized for controlling a transition-metal catalyst electronically. The 1b-ligated Rh catalyst showed excellent catalytic activity with high % ee for asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyls at 20 °C. The strong π-acceptor ability of 1b induces transmetalation of arylboronic acid to catalyst precursor [RhCl(1b)]2 directly in the first step of the catalytic cycle.

The existence of the intermolecular interaction in CDCl3 between oxygen of MeOH and the C6F5 group is demonstrated.

α,α,α-Trifluoroacetophenone (2), which is susceptible to noncatalytic reduction by BH3, could be reduced to chiral alcohol up to 90% ee by using electronically tuned-CBS catalyst (1) with BH3. The enantioselectivities highly correlated with the differential orbital energies between 1–BH3 adduct and 2, which were calculated by DFT method.

The existence of the intermolecular interaction in CDCl3 between oxygen of MeOH and the C6F5 group is demonstrated.