Rhodacarborane complexes with a triphenylphosphonium substituent as efficient catalysts for on-water transfer hydrogenation of carbonyl compounds

2026-05-01

PRE

Mikhail M. Vinogradov *

Nelyubina, Yulia V.

Ivan A. Godovikov

Godovikova, Maria I.

Kharitonov, Vladimir B.

Evgeniya Podyacheva

Rodionov, Alexey N.

DOI：10.1039/d6dt00999a

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Two isomeric rhodacarborane chloride complexes [1,8-Bn-2-2,2-Cl-2-X-PPh3-2,1,8-closo-RhC2B9H8](2) (X = 7 and 11) were synthesized. One of them (X = 7) exhibits high catalytic activity in the on-water reduction of aromatic and aliphatic aldehydes and ketones with ammonium formate to the corresponding alcohols with a 0.2 mol% loading. The enantiopure form of a planar chiral catalyst was obtained via isolation of a cyclometallated complex with (S)-proline. The enantiopure form of the catalyst affords alcohols with enantiomeric excess when prochiral ketones are used in the reaction. The same catalyst is active in the Oppenauer-type oxidation of (+/-)-1-phenylethanol with acetone in the presence of K2CO3. The transfer hydrogenation is accompanied by in situ reversible cyclometallation of the catalytic species engaging the ortho-CH bonds of PPh3.

Keywords:

OPPENAUER-TYPE OXIDATION

HALF-SANDWICH COMPLEXES

MOLECULAR-STRUCTURE

THERMAL REARRANGEMENT

ALKENE ISOMERIZATION

GAMMA-VALEROLACTONE

REACTIVITY

METAL

LIGAND

METALLACARBORANES

Rhodacarborane complexes with a triphenylphosphonium substituent as efficient catalysts for on-water transfer hydrogenation of carbonyl compounds

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