Энантиоселективный синтез β-гидроксикарбонильных соединений из альдегидов и кетонов под действием пролинсодержащих органокатализаторов, иммобилизованных в ионных жидкостях и на полиэлектролитах тема диссертации и автореферата по ВАК РФ 02.00.03, кандидат химических наук Кучеренко, Александр Сергеевич

• Кучеренко, Александр Сергеевич
• кандидат химических наук
• 2008

Оглавление диссертации кандидат химических наук Кучеренко, Александр Сергеевич

СПИСОК СОКРАЩЕНИЙ

I. ВВЕДЕНИЕ

II. Методы регенерации органокатализаторов асимметрической альдольной реакции (литературный обзор)

II. 1 Энантиоселективный органокатализ - перспективное направление развития органической химии

II.2 Механизм енаминового катализа альдольной реакции

II.3 Альдольные реакции под действием иммобилизованных органокатализаторов

II.3.1 Альдольные реакции под действием органокатализаторов, иммобилизованных без участия ковалентных связей

II.3.1.1 Альдольные реакции в ионных жидкостях и полиэтиленгликоле

II.3.1.2 Альдольные реакции под действием органокатализаторов нанесенных на полимеры

II.3.2. Альдольные реакции под действием органокатализаторов, содержащих ковалентно связанные полимерные или ионные фрагменты

II.3.2.1 Органокатализаторы, содержащие ковалентно связанные полимерные группы

II.3.2.2 Органокатализаторы, содержащие ковалентно связанные ионные группы

Заключение диссертации по теме «Органическая химия», Кучеренко, Александр Сергеевич

V. ВЫВОДЫ

1. Разработан эффективный метод синтеза хиральных (3-гидроксикарбонильных соединений различного строения под действием гетерогенной каталитической системы (8)-пролин/поли-(диметилдиаллиламмоний) гексафторфосфат. Иммобилизация органокатализатора на полиэлектролите обеспечивает легкость регенерации и многократное (не менее 6 раз) его использование без уменьшения активности и энантиоселективности.

2. Предложена высокоактивная регенерируемая каталитическая система 1(К),2(Я)-бис[(8)-пролинамидо]циклогексан/Ьгтт[ВР4], позволяющая проводить прямую асимметрическую альдольную реакцию между альдегидами и кетонами в условиях 3-кратного избытка кетона - значительно меньшего, чем требуется в аналогичной реакции, катализируемой (З)-пролином.

3. Разработан эффективный метод проведения асимметрической альдольной реакции между альдегидами и кетонами в системе ИЖ/вода (1:1 объем.). Добавление воды повышает скорость, диастереоселективность и, в некоторых случаях, энантиоселективность реакции, а также увеличивает срок службы каталитической системы.

4. На примере асимметрического гидрирования эфира левулиновой кислоты в у-валеролактон показано, что предложенный подход к иммобилизации хиральных катализаторов путем их нанесения на твердые органические полиэлектролиты носит общий характер и может быть применен для регенерации металлокомплексных катализаторов.

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