Russian Chemical Bulletin, International Edition, Vol. 59, No. 2, pp. 434—440, February, 2010 434 Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 425—430, February, 2010. 1066-5285/10/5902-0434 © 2010 Springer Science+Business Media, Inc. Phosphorodiamidite derivatives of 1,1´-bi-2-naphthol containing stereogenic phosphorus atoms as ligands in enantioselective catalysis K. N. Gavrilov, a A. S. Safronov, b E. A. Rastorguev, a N. N. Groshkin, a S. V. Zheglov, a A. A. Shiryaev, a M. G. Maksimova, a P. V. Petrovskii, b V. A. Davankov, b and M. T. Reetz c a S. A. Esenin Ryazan State Pedagogic University, 46 ul. Svobody, 390000 Ryazan, Russian Federation. Fax: +7 (491 2) 77 5498. E-mail: k.gavrilov@rsu.edu.ru b A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilova, 119991 Moscow, Russian Federation. Fax: +7 (495) 135 6471. E-mail: vxd2000@mail.ru c Max-Planck-Institute For Coal Research, 1 Kaiser-Wilhelm-Platz, 45470 Mülheim an der Ruhr, Germany.* Fax: (49 208) 306 2985. E-mail: reetz@mpi-muelheim.mpg.de 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%. Key words: P *-chiral phosphorodiamidites, rhodium complexes, palladium complexes, platinum complexes, catalysts, asymmetric allylation, asymmetric hydrogenation. The modern asymmetric metal complex catalysis is one of the most effective and environmentally safe meth- ods for the synthesis of optically pure organic and hetero- organic compounds. In addition to the well-known appli- cation in pharmaceutical chemistry, this method is suc- cessfully used in the synthesis of fragrance compounds, plant protection chemicals, individual stereoisomeric poly- mers, and liquid crystals. 1—4 To achieve virtually quanti- tative chemical and optical yields in enantioselective cat- alytic transformations, it is necessary to carefully opti- mize various reaction parameters, primarily, to correctly choose the corresponding ligand group and to rationally design each representative of this group. 5 P,P-Bidentate phosphines belong to a class of effective phosphorus-con- taining stereoselectors. At the same time, recent studies have shown 6—11 that phosphite-type P,P-bidentate ligands are highly competitive with the above-mentioned com- pounds and have advantages in that they can easily be synthesized from readily accessible precursors, are resis- tant to oxidation, have a pronounced π-acidity, and are less expensive. In particular, bis-phosphite derivatives of the known chiral agent 1,1´-bi-2-naphthol (BINOL) can be considered as promising stereoinducers. 12 Thus, phos- phite ligands L A—C containing the 1,3,2-dioxaphosphep- ine rings based on BINOL, its octahydrogenated deriva- tive (H 8 -BINOL), or various 2,2´-dihydroxy-1,1´-biphe- nyls were successfully used in the Cu-catalyzed conjugat- ed addition, 13—17 the Co-catalyzed Pauson–Khand reac- tion, 18 and the Rh-catalyzed hydroformylation. 19,20 Phos- phites L D—F containing the 1,3,2-dioxaphosphorinane and 1,3,2-dioxaphospholane rings based on chiral 1,3- and 1,2-diols appeared to be ineffective stereoselectors. Thus, the ee of no higher than 40% was achieved with their use in the Rh-catalyzed hydroformylation of styrene. 21—23 Hence, the synthesis of new effective phosphite-type BINOL-based P,P-bidentate ligands remains an impor- tant problem. Previously, 24,25 we have described the syn- thesis of diastereomeric P*,P*-bidentate phosphorodi- amidites containing 1,3,2-diazaphospholidine rings based on 1,4:3,6-dianhydro-D-mannite and reported on the use of these compounds in catalytic asymmetric reactions. It should be noted that P*-chiral 1,3,2-diazaphospholidines belong to an attractive group of optically active phosphoro- diamidite ligands. In particular, these ligands have bal- anced electronic characteristics because they are both good π-acceptors (due to the accessibility of low-lying π* PN orbitals) and good σ-donors. The inclusion of the phos- phorus atom in the five-membered ring enhances the re- sistance of the ligands to oxidation and hydrolysis, and the * Max-Planck-Institut für Kohlenforschung, 1 Kaiser-Wilhelm- Platz, 45470 Mülheim an der Ruhr, Germany.