Nowa katalityczna metoda syntezy 1-borylo-4-metaloido(Si, Ge, B)butadienów oraz innych pochodnych 1-borylobutadienów
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Date
2015-06-16
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The new catalytic method for the synthesis of 1-boryl-4-metalloid(Si, Ge, B)butadienes and other derivatives of 1-borylbutadienes
Abstract
Podstawowym założeniem pracy doktorskiej było badanie reaktywności etynylometaloidów (etynylogermananów, etynyloboranów, alkinów z różnymi grupami funkcyjnymi) w reakcji kodimeryzacji. Otrzymane produkty dzięki obecności tych samych lub różnych metaloidów w skrajnych pozycjach stanowić będą ciekawe reagenty dla syntezy organicznej. Sprawdzona zostałą również reaktywność dwuetynylopodstawionych alkinów, sililo- i germyloalkinów, które do tej pory nie były testowane w tego typu reakcji. Dodatkowym elementem pracy była także funkcjonalizacja alkinylosilseskwioksanów, klatkowych związków krzemoorganicznych o hybrydowych właściwościach nieorganiczno-organicznych, która pozwoli wprowadzić fragment borylobutadienylowy w ich strukturę.
W pracy doktorskiej przeprowadzono również dokładne badania mechanistyczne w oparciu o kwantochemiczne metody teorii funkcjonału gęstości (DFT) i pomiary kinetyczne dla modelowych reakcji sprzęgania terminalnych krzemo-, germylo- i borylopodstawionych alkinów z winyloboranami, a także określić etap limitujący szybkość tego procesu. Badania te potwierdziły wyniki eksperymentalnych prac uzyskanych na drodze reakcji stechiometrycznych sililoalkinów z winyloboranami, na podstawie których zaproponowany został mechanizm. Dodatkowo badania mechanistyczne zostały rozszerzone o szereg kolejnych reakcji równomolowych z etynylogermananami, tak by można było szczegółowo zrozumieć mechanizm tego procesu.
The main aim of the study presented within the doctoral dissertation was to establish the reactivity of ethynylmetalloides (ethynylgermananes, ethynylboranes, alkynes with different functional groups) in the co-dimerization reaction. The products obtained, owing to the presence of the same or different metalloids in extreme positions of their molecules were expected to be interesting reagents for organic synthesis. The reactivity of diethynylsubstituted alkynes, silyl and germylalkynes, which until now has not been tested in this type of reactions, was also checked. Another challenge of the study was functionalization of ethynylsiloxysilsesquioxanes, cage organosilicon compounds of hybrid inorganic-organic properties, which was expected to permit the introduction of a borylobutadienyl group into the structure of these compounds. Detailed mechanistic studies, based on the density functional theory methods (DFT) were performed and kinetic measurements were made for the model coupling reaction of terminal silil-, boryl- and germylsubstituted alkynes with vinylboronates, which permitted determination of the rate limiting step of the process. These studies confirmed the results of experimental work for the stoichiometric reaction of sililalkynes with vinylboronates, for which the mechanism has been developed. In addition, mechanistic studies were extended to a number of other reactions with equimolar ethynylgermananes, to contribute to full understanding of the chemistry of this process.
The main aim of the study presented within the doctoral dissertation was to establish the reactivity of ethynylmetalloides (ethynylgermananes, ethynylboranes, alkynes with different functional groups) in the co-dimerization reaction. The products obtained, owing to the presence of the same or different metalloids in extreme positions of their molecules were expected to be interesting reagents for organic synthesis. The reactivity of diethynylsubstituted alkynes, silyl and germylalkynes, which until now has not been tested in this type of reactions, was also checked. Another challenge of the study was functionalization of ethynylsiloxysilsesquioxanes, cage organosilicon compounds of hybrid inorganic-organic properties, which was expected to permit the introduction of a borylobutadienyl group into the structure of these compounds. Detailed mechanistic studies, based on the density functional theory methods (DFT) were performed and kinetic measurements were made for the model coupling reaction of terminal silil-, boryl- and germylsubstituted alkynes with vinylboronates, which permitted determination of the rate limiting step of the process. These studies confirmed the results of experimental work for the stoichiometric reaction of sililalkynes with vinylboronates, for which the mechanism has been developed. In addition, mechanistic studies were extended to a number of other reactions with equimolar ethynylgermananes, to contribute to full understanding of the chemistry of this process.
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Wydział Chemii UAM w Poznaniu: Zakład Chemii Metaloorganicznej
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Keywords
reakcja kodimeryzacji, Co-dimerization, 1-borylobutadieny, 1-borylo-4-metaloidobuta-1, 1-borylbutadienes, 3-dieny, 3-dienes, obliczenia DFT, DFT calculations, badania kinetyczne, kinetic studies