Доклады Академии наукДоклады Академии наук0869-5652The Russian Academy of Sciences1176510.31857/S0869-56524843307-311Research ArticleSolid state catalytic hydrogen exchange for deuterium in cycloprolylglycineDadayanA. K.dak.img.ras@gmail.comBorisovYu. A.dak.img.ras@gmail.comBocharovE. V.dak.img.ras@gmail.comZolotarevYu. A.dak.img.ras@gmail.comNagaevI. Yu.dak.img.ras@gmail.comMyasoedovN. F.dak.img.ras@gmail.com1504201948433073111504201915042019Copyright © 2019,2019<p>The reaction of spillover hydrogen (SH) with cyclopropylglycine (cPG) in high-temperature solid-state catalytic hydrogen isotope exchange (HTCIE) has been studied experimentally and using density functional theory (DFT). NMR spectroscopy and mass spectrometry have shown a high regioselectivity and stereoselectivity for the reaction of spillover hydrogen with cPG fragments. The Gly fragment has been shown to be the most reactive in HTCIE, for which high stereoselectivity of substitution of hydrogen by deuterium has been demonstrated.</p>quantum-chemical calculationDFT B3LYP/6-31G* methodactivation energyhydrogen isotope exchangespillover hydrogenквантово-химический расчетметод DFT B3LYP/6-31G*энергия активацииизотопный обмен водородаспилловер водорода[Boudart M., Vannice M.A., Benson J.E. // J. Phys. Chem. 1969. V. 64. P. 171–177.][Conner W.C., Falconer J.L. // Chem. Rev. 1995. V. 95. P. 759–788.][Yang M., Nakamura I., Fujuimoto K. // J. Appl. Catal. General. 1996. V. 144. P. 221–235.][Stumbo A.M., Grande P., Delmon B. // Stud. Surface Sci. and Catalysis. 1997. V. 112. P. 211–220.][Roessner F., Roland U., Braunschweig T. // J. Chem. Soc. Faraday Trans. 1995. V. 91. P. 1536–1545.][Zolotarev Yu.A., Dadayan A. K., Borisov Yu.A., Kozik V.S. Chem. Revs. 2010. V. 110. P. 5425–5446.][Zolotarev Yu.A., Dorokhova E.M., Nezavibatko V.N., Borisov Yu.A., Rosenberg S.G., Myasoedov N.F. // Amino Acids. 1995. V. 8. P. 353–365.][Zolotarev Yu.A., Dadayan A. K., Borisov Yu.A.,][Kozik V.S., Nazimov I.V., Ziganshin R.H., Bocharov E.V., Chizhov A.O., Myasoedov N.F. // J. Phys. Chem. C. 2013. V. 117. № 33. P. 16 878–16 884.][Gaussian 09W, Vers. 7.0, Copyright 1995-09 Gaussian, Inc.][Gonzalez C., Schlegel H.B. // J. Phys. Chem. 1990. V. 94. № 14. P. 5523–5527.][Schlegel H.B., Robb M.A. // Chem. Phys. Lett. 1982. V. 93. № 1. P. 43–46.][Schlegel H.B. Geometry Optimization on Potential Energy Surfaces. In: Modern Electronic Structure Theory. Singapore: World Sci. Publ., 1995.]