Сравнение каталитических систем на основе комплексов Ni, Pd и Au в атом-экономичных реакциях образования связи углерод-сера тема диссертации и автореферата по ВАК РФ 02.00.03, кандидат химических наук Залесский, Сергей Сергеевич

• Залесский, Сергей Сергеевич
• кандидат химических наук
• 2013

Оглавление диссертации кандидат химических наук Залесский, Сергей Сергеевич

Содержание

Список использованных сокращений

1. Введение

2. Литературный обзор

2.1 Присоединение тиолов и селенолов к алкинам в отсутствие металлсодержащих катализаторов

2.1.2 Реакции нуклеофильного присоединения

2.2 Присоединение тиолов и селенолов к алкинам, катализируемое комплексами Ni и Pd

2.3 Реакции образования связей C-S и C-Se катализируемые комплексами золота

3. Обсуждение результатов

3.1 Образование связи C-S, катализируемое комплексами никеля.. - 42 -

3.2 Образование связи C-S, катализируемое комплексами палладия- 51 -3.2.1 РсЬсИэаз как источник растворимых комплексов и наночастиц

палладия для каталитических реакций

3.2.3 Адаптивная перестройка паноразмерного катализатора в реакции гидрохалькогенирования алкинов

3.3 Образование связи C-S с участием комплексов золота

3.3.1 Разработка универсального метода синтеза предшественников катализаторов на основе Au(I)

3.3.2 Исследование каталитической активности синтезированных комплексов и наночастиц Аи°

3.3.3 Синтез и реакционная способность комплекса Ph3PAuMe - 104 -

3.3.4 Синтез и реакционная способность комплексов Ph3PAuZPh- 108 -

3.3.5 Анализ возможных механизмов образования связи C-S при участии комплексов золота

4. Экспериментальная часть

Эксперимент к разделу 3.1

Эксперимент к разделу 3.2.1

Эксперимент к разделу 3.2.2

Эксперимент к разделу 3.2.3

Эксперимент к разделу 3.3

5. Результаты работы

6. Благодарности

7. Список литературы

Список использованных сокращений

КССВ - константа спин-спинового взаимодействия РСА - рентгеноструктурный анализ

COSY - гомоядерная корелляционная спектроскопия ЯМР (COrellation Spectroscopy)

COSY-LR - гомоядерная корреляционная спектроскопия ЯМР, оптимизированная для наблюдения дальних констант спин-спинового взаимодействия (COSY-Long Range)

DBA - дибензилиденацетон (DiBenzylideneAcetone)

DOSY - диффузионно-упорядоченный спектр ЯМР (Diffusion-Ordered SpectroscopY)

NHC - N-гетероциклический карбен (N-Heterocyclic Carbene) NOE - ядерный эффект Оверхаузера (Nuclear Overhauser Effect) NOESY - ЯМР-спектроскопия ядерного эффекта Оверхаузера (Nuclear Overhauser Effect SpectroscopY)

HMBC - гетероядерная корреляционная спектроскопия ЯМР для наблюдения дальних КССВ (Heteronuclear Multiple Bond Correlation)

HRMS - масс-спектрометрия высокого разрешения (High-Resolution Mass Spectrometry)

HSQC - гетероядерная корреляционная спектроскопия ЯМР для наблюдения прямых КССВ (Heteronulear Single-Quantum Coherence)

PGSE - импульсное градиентное спиновое эхо ЯМР (Pulse Gradient Spin Echo)

PGSTE - импульсное градиентное стимулированное спиновое эхо ЯМР (Pulse Gradient STimulated Echo)

Введение диссертации (часть автореферата) на тему «Сравнение каталитических систем на основе комплексов Ni, Pd и Au в атом-экономичных реакциях образования связи углерод-сера»

1. Введение

Соединения, содержащие фрагмент С=С-Ъ, Ъ = Б, Бе - винилхалькогениды - являются ценными реагентами в органическом синтезе [1,2,3]. Комплексы бис-селензамещенных алкенов с переходными металлами активно исследуются как предшественники полупроводниковых материалов в материаловедении [4], а винилселениды в последнее время активно изучаются на предмет их биологической активности и применения в медицине и фармакологии [5].

На сегодняшний день существует ряд обзоров [1г,2а,2б,3в,6] и монографий [7], описывающих получение винилхалькогенидов. Наиболее важные и общие методы построения фрагмента С=С-Ъ приведены на схеме (Схема 1).

Это электрофильное сульфенилирование алкинов {путь 1), алленов {путь 2), а также алкенов с последующим элиминированием {путь 3), алкилирование халькоген-енолятов {путь 4), алкилирование

металлорганических реагентов {путь 5), нуклеофильное замещение при Бр углеродном атоме {путь 6), реакция Виттига {путь 7) и, наконец, присоединение молекул со связями Ъ-Ъ и Ъ-Н к алкинам {путь 8).

п\ть 8

Заключение диссертации по теме «Органическая химия», Залесский, Сергей Сергеевич

5. Результаты работы

1) Было показано, что определяющую роль в селективности катализируемого комплексами N1 присоединения тиолов к алкинам играет стадия внедрения алкина по связи N1-8 и дальнейшие пути трансформации полученного винильного комплекса. На основании предложенного механизма была разработана методика каталитического присоединения, позволившая получать продукты с высокими выходами при 100% атомной эффективности.

2) Продемонстрировано, что 31Р Б08У ЯМР является быстрым и информативным методом для изучения механизмов каталитических превращений. Данный метод был успешно использован для идентификации моноядерных и биядерных комплексов палладия - ключевых интермедиатов в реакции присоединения дисульфидов к алкинам.

3) Был разработан наноразмерный катализатор на основе палладия для селективного извлечения халькогенидов из смесей. Обнаруженный эффект адаптивной перестройки катализатора позволяет с исключительной селективностью извлекать целевые соединения на фоне высокой концентрации примесей, даже в случае изменяющегося во времени состава реакционной массы.

4) Был предложен и реализован удобный метод для синтеза широкого круга растворимых комплексов золота(1) и наночастиц золота из единого предшественника без использования сложных экспериментальных процедур. В рамках предложенной концепции "каталитического конструктора" были получены соединения Аи(1) и частицы Аи(0) из простых и доступных предшественников.

5) Впервые выделены уникальные винильные комплексы Аи(1), подтверждающие ключевую роль винилиденовых комплексов в каталитических реакциях. Показано, что распад данных комплексов в кислых условиях приводит к образованию линейных винилсульфидов - продуктов присоединения тиолов к алкинам.

6. Благодарности

Хочу сказать большое спасибо членам научной группы Ананикова В. П. за ценные замечания и дискуссии, а также за поддержку и чувство юмора:

Хемчяну JI.JL; Ивановой Ю.В.; Кашину A.C.; Ромашову J1.B.; Орлову Н. В.

Особая благодарность:

- Качале В.В. за обучение ЯМР-спектроскопии;

- Шулишову Е.В. за ценные советы и поддержку;

- Чижову А.О. за съемку спектров HRMS;

- Корлюкову A.A., Архипову Д.Е. (ИНЭОС РАН) - за проведение рентгеноструктурных исследований.

Отдельно я хотел бы выразить огромную признательность моим Учителям - Ананикову В.П. и Белякову П.А. Их советы и поддержка помогали как в научных исследованиях, так и в аспирантской жизни.

Список литературы диссертационного исследования кандидат химических наук Залесский, Сергей Сергеевич, 2013 год

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