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P*-Mono- and P*,P*-bidentate phosphorodiamidites containing the (S a )-1,1′-binaphthyl core and 1,3,2-diazaphospholidine rings were synthesized. The use of these compounds in the rhodium-catalyzed asymmetric hydrogenation, as well as in the palladium- and platinum-catalyzed asymmetric alkylation and amination, resulted in the formation of the products with ee of up to 99%.

A chiral P,N-bidentate aryl phosphite ligand containing peripheral (R)-(+)-camphor-derived ketimine and its rhodium(I) and palladium(II) chelate complexes were synthesized for the first time. These compounds were found to be suitable for asymmetric allylic substitution. The Pd-catalyzed sulfonylation of 1,3-diphenylallyl acetate with sodium p-toluenesulfinate gave the product in 73% ee; in the alkylation of the same substrate with dimethyl malonate, the ee was 94%. These ee values are higher than the enantioselectivity achieved with the known phosphine analogs.

The complex formation of bi- and tricyclic hydrophosphorane derivatives of isoleucinol with [Pt(COD)Cl2], [Rh(CO)2Cl]2, and [Rh(THF)2(COD)]+BF4– (COD is cycloocta-1,5-diene) was investigated. In all cases, bicyclic hydrospirophosphorane selectively forms the metal chelates [M(η2-P∩N)(X)Cl] (M = Pt, X = Cl; M = Rh, X = CO) and [Rh(η2-P∩N)(COD)]+BF4–. («∩» denotes the residue of the hydrospirophosphorane ligand, which does not contain the P and N atoms). In addition, tricyclic hydrophosphorane (L) generates the phosphoranide complexes [Pt(η1-L)(COD)Cl]+Y– (Y = Cl or BF4). The structures of the new compounds were established by IR spectroscopy, 31P, 13C, 1H, 2H, 11B, 19F, and 195Pt NMR spectroscopy, and plasma-desorption and electrospray ionization mass spectrometry. The possible mechanism of coordination of hydrophosphoranes is discussed.

The asymmetric synthesis of methyl 2-phenyl-2-(2-phenyl-ortho-carboran-1-yl)pent-4-enoate was carried out by palladium-catalyzed allylation in the presence of amino phosphites of the type (RO)2P—O—CH2—CHR"—NR″2 as chiral ligands.

Reactions of phosphoramidites based on (−)-ephedrine and [(1S)-endo]-(−)-borneol with the complexes M(COD)Cl2 (M is Pd or Pt, and COD is cycloocta-1,5-diene) were studied. The formation ofcis andtrans complexes of the general formulas MCl2L2 and M2Cl2(μ-Cl)2L2 was observed. The structures of the resulting compounds were established by31P,13C, and195Pt NMR and IR spectroscopy and by plasma desorption mass spectrometry.

aN. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp.. 117913 Moscow, Russian Federation. fax: 007 (095) 135 5328 bS. A. Esenin Ryazan State University of Education, 46 ul. Svobody, 390000 Ryazan, Russian Federation. Fax: 007 (091 2) 44 4390. E-maih chem@ttc.ryazan.ru CA. K Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky prosp., 117912 Moscow, Russian Federation. Fax: 007 (095) 23