ChemInform Abstract: Synthesis and X-Ray Structure of Metalated Rhodium(II) Catalysts with a Chiral Phospholane.

The reaction of Rh2(O2CR)4 (R = CH3, CF3) with the chiral phosphane (2S,5S)-2,5-dimethyl-1-phenylphospholane (PC*H), results in the formation of two diastereoisomers of Rh2(O2CCR)2(PC*)2, with (P) and (M) configuration. These can easily be isolated by chromatographic methods to obtain enantiomerically pure RhII compounds. Preliminary catalytic studies have shown that they induce moderate asymmetry in the cyclization of 5-aryl-1-diazo-2-pentanones and 1-diazo-5-hexen-2-one. X-ray analysis of the (M) diastereoisomer with formula Rh2(O2CCCH3)2(PC*)2 is reported. The crystallographic parameters are as follows: space group P21212 (orthorhombic) with a = 12.1347(11) A, b = 14.5870(13) A, c = 9.81…

Book Review: Comprehensive Organometallic Chemistry. The Synthesis, Reactions and Structures of Organometallic Compounds. Nine volumes. Editors G. Wilkinson, F. G. A. Stone, E. W. Abel

Synthesis and X-ray structure of metalated Rhodium(II) catalysts with a chiral phospholane

The reaction of Rh2(O2CR)4 (R = CH3, CF3) with the chiral phosphane (2S,5S)-2,5-dimethyl-1-phenylphospholane (PC*H), results in the formation of two diastereoisomers of Rh2(O2CCR)2(PC*)2, with (P) and (M) configuration. These can easily be isolated by chromatographic methods to obtain enantiomerically pure RhII compounds. Preliminary catalytic studies have shown that they induce moderate asymmetry in the cyclization of 5-aryl-1-diazo-2-pentanones and 1-diazo-5-hexen-2-one. X-ray analysis of the (M) diastereoisomer with formula Rh2(O2CCCH3)2(PC*)2 is reported. The crystallographic parameters are as follows: space group P21212 (orthorhombic) with a = 12.1347(11) A, b = 14.5870(13) A, c = 9.81…