Хиральные комплексы переходных металлов с хелатными азотными лигандами в асимметрическом гидрировании с переносом водорода

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.

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