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New homochiralortho-palladated matrix bearing a bulky substituent at the carbon stereocenter
Authors:V. V. Dunina  M. Yu. Kazakova  Yu. K. Grishin  O. R. Malyshev  E. I. Kazakova
Affiliation:(1) Department of Chemistry, M. V. Lomonosov Moscow State University, Vorob'evy Gory, 119899 Moscow, Russian Federation;(2) N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky prosp., 117913 Moscow, Russian Federation;(3) Chemicobiological Department, Syktyvkar State University, 120 ul. Petrozavodskaya, 167005 Syktyvkar, Russian Federation
Abstract:A new homochiral dimericortho-palladated complex bearing a bulkytert-butyl substituent at the carbon stereocenter was synthesized from optically activeN,N-dimethyl-α-tert-butylbenzylamine. Regioselective activation of only the aromatic C−H bond was shown to occur during the cyclometallation process proceeding under very mild conditions due to steric effects. Spectral characteristics of mononuclear derivatives of the new dimeric complex indicate that the five-membered palladacycle exists predominantly in one of two possible chiral conformations with the axial position of thetert-butyl substituent. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1375–1384, July, 1997.
Keywords:ortho-palladation  regioselectivity  optical resolution  conformation of palladacycle  chiroptical properties
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