vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/2227-2925-2019-9-4-621-634vuzbiochemi-257Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESХиральные комплексы переходных металлов с хелатными азотными лигандами в асимметрическом гидрировании с переносом водородаChiral complexes of transition metals with chelating nitrogen ligands in asymmetric hydrogenation with hydrogen transferБадыроваН. М.BadyrovaN. M.

Бадырова Наталия Моисеевна, к.х.н., доцент

664074, г. Иркутск, ул. Лермонтова, 83

Nataliya M. Badyrova, Cand. Sci. (Chemistry), Associate Professor

83, Lermontov St., Irkutsk 664074

n.m.badyrova@ex.istu.eduНиндаковаЛ. О.NindakovaL. O.

Ниндакова Лидия Очировна, д.х.н., старший научный сотрудник, профессор

664074, г. Иркутск, ул. Лермонтова, 83

Lidiya O. Nindakova, Dr. Sci. (Chemistry), Senior Researcher, Professor

83, Lermontov St., Irkutsk 664074

nindakova@istu.eduИркутский национальный исследовательский технический университетРоссияIrkutsk National Research Technical UniversityRussian Federation20190501202094621634Copyright © Бадырова Н.М., Ниндакова Л.О., 20202020Бадырова Н.М., Ниндакова Л.О.Badyrova N.M., Nindakova L.O.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/257

Реакция каталитического гидрирования с переносом водорода ненасыщенных С = С и С = О связей в органических соединениях в присутствии оптически активных растворимых комплексов переходных металлов с азотсодержащими мультидентатными лигандами нашла широкое распространение в последние два десятилетия. Цель данной обзорной статьи – привести сведения по наиболее эффективным и перспективным металлокомплексным катализаторам асимметрического гидрирования с переносом водорода, предложенным в последние 10–15 лет. Поскольку активность и селективность катализаторов на основе комплексов переходных металлов в значительной степени зависят от их состава и структуры, то дизайн лигандов, наличие или отсутствие стереогенных центров, устойчивость и конфигурация хелатной системы лиганда, природа дентатных атомов в них крайне важны. Усилия ученых сосредоточены на синтезе и применении в качестве лигандов оптически активных диаминов и аминоспиртов с sp3 -гибридизованными дентатными атомами, не подвергающимися окислению в координационной сфере переходных металлов подобно фосфиновым лигандам, сохраняя в то же время высокую стереогенность. В отдельную группу выделены оптически активные лиганды с sp2 -азотными атомами, содержащие азометиновую связь С = N, оксазолиновые фрагменты, которые в комплексах с переходными металлами показывают высокую стабильность в реакции каталитического гидрирования с переносом водорода. Стереоселективность катализаторов в отдельных случаях повышается с увеличением дентатности азотсодержащих лигандов, в частности, эффективны N-гетероциклические N,H,C-лиганды в составе комплексов Rh (III), Ru (II) комплексы с тридентатными N, N, N-лигандами c хиральными оксазолиновыми фрагментами, C, N, N-рутениевые комплексы. В обзоре катализаторы сгруппированы по дентатности лигандов (от 2 до 6), приведены сравнительные данные по активности катализаторов и стереоселективности реакций, обсуждается влияние строения хиральных лигандов на каталитические характеристики металлокомплексов.

Авторы заявляют об отсутствии конфликта интересов.

The reaction of catalytic hydrogenation involving hydrogen transfer through unsaturated C = C and C = O bonds in organic compounds in the presence of optically active soluble complexes of transition metals with nitrogen-containing multidentate ligands has recently gained increased popularity. This review is aimed at generalising available information on the most effective and promising metal complex catalysts for asymmetric hydrogenation involving hydrogen transfer, which have been proposed in the past 10–15 years. Since the activity and selectivity of catalysts based on transition metal complexes are largely dependent on their composition and structure, the design of ligands, the presence or absence of stereogenic centres, the stability and configuration of the chelating ligand system, the nature of the dentate atoms present therein are extremely important. Researchers worldwide have been largely focused on the synthesis and use such ligands, as optically active diamines and aminoalcohols with sp3 -hybridized dentate atoms. These compositions are not oxidized in the coordination sphere of transition metals compared to phosphine ligands, at the same time as maintaining a high level of stereogenicity. Optically active ligands with sp2 nitrogen atoms containing the C = N azomethine bond and oxazoline fragments have been considered as a separate group. In complexes with transition metals, these ligands exhibit a high stability in the catalytic hydrogenation reaction with hydrogen transfer. The stereoselectivity of catalysts in some cases increases with an increase in the denticity of nitrogen-containing ligands. Among them are N-heterocyclic N, H, C–ligands in the Rh (III) complexes; Ru (II) complexes with tridentate N, N, N–ligands with chiral oxazoline fragments; C, N, N–ruthenium complexes. In this review, we grouped catalysts by ligand denticity (from 2 to 6). Comparative data on the activity of various catalysts and the stereoselectivity of respective reactions is provided. The effect of the structure of chiral ligands on the catalytic characteristics of metal complexes is discussed.

The authors declare no conflict of interests regarding the publication of this article.

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The authors declare that there are no conflicts of interest present.