A facile synthesis of 1,1-bis(silyl)ethenes.
TL;DR: Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2, 4-disilacycloheptane with excellent selectivity and good yield.
Abstract: Symmetrical 1,1-bis(silyl)ethenes have been easily prepared via ruthenium complex-catalyzed silylative coupling cyclization of 1,2-bis(dimethylvinylsiloxy)ethane to give 2,2,4,4-tetramethyl-3-methylene-1,5-dioxa-2,4-disilacycloheptane with excellent selectivity and good yield, followed by its reaction with Grignard reagents. The cyclic product can also be effectively transformed into cyclic carbosiloxane, 2,2,4,4,6,6,8,8-octamethyl-3,7-dimethylene-1,5-dioxa-2,4,6,8-tetrasilacyclooctane.
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TL;DR: In this article, the mechanism of homogeneous catalysis for silylation of alkenes and silylalkynes with late transition metal complexes is discussed. But the authors focus on the synthesis of substituted vinyl-silicon functionalities.
369 citations
TL;DR: It has been shown that silylative coupling of olefins can be extended over both other vinylmetalloid derivatives (double bond C-E) as well as the activation of triple bond C -H, double bond C aryl-H, and -O-H bond of alcohols and silanols.
Abstract: In the Account given herein, it has been shown that silylative coupling of olefins, well-recognized as a new catalytic route for the activation of double bond C-H bond of olefins and double bond C-Si bond of vinylsilicon compounds with ethylene elimination, can be extended over both other vinylmetalloid derivatives (double bond C-E) (where E = Ge, B, and others) as well as the activation of triple bond C-H, double bond C aryl-H, and -O-H bond of alcohols and silanols. This general transformation is catalyzed by transition-metal complexes (mainly Ru and Rh) containing or initiating TM-H and/or TM-E bonds (inorganometallics). This new general catalytic route for the activation of double bond C-H and triple bond C-H as well as double bond C-E bonds called metallative coupling or trans-metalation (cross-coupling, ring-closing, and polycondensation) constitutes an efficient method (complementary to metathesis) for stereo- and regioselective synthesis of a variety of molecular and macromolecular compounds of vinyl-E (E = Si, B, and Ge) and ethynyl-E (E = Si and Ge) functionality, also potent organometallic reagents for efficient synthesis of highly pi-conjugated organic compounds. The mechanisms of the catalysis of this deethenative metalation have been supported by equimolar reactions of TM-H and/or TM-E with initial substances and reactions with deuterium-labeled reagents.
73 citations
TL;DR: In this article, a review of the development and development of highly efficient and selective methods for the synthesis of π-conjugated arylvinyl derivatives, based on sequential catalytic reactions of organometallic reagents, have been the subject of extensive study.
43 citations
TL;DR: The development of highly selective methods for the synthesis of functionalized olefins based on sequential catalytic reactions of organometallic reagents has been the subject of extensive study because of their versatile applications in organic synthesis and materials science as discussed by the authors.
Abstract: The development of highly selective methods for the synthesis of functionalized olefins, based on sequential catalytic reactions of organometallic reagents, has been the subject of extensive study because of their versatile applications in organic synthesis and materials science. The silylative coupling of olefins with vinyl-substituted organosilicon compounds (discovered in our group) represents one of the most efficient and straightforward methods for the synthesis of stereodefined alkenylsilanes and bis(silyl)alkenes, which are particularly attractive scaffolds for further transformations including palladium-catalyzed cross-coupling with organic halides (Hiyama coupling) or electrophile-induced desilylation. The article highlights the recent developments and covers the literature mainly from the last decade in the sequential (also one-pot) synthetic strategies including ruthenium-catalyzed silylative coupling followed by desilylative cross-coupling, acylation and halogenation, leading to stereodefined organic derivatives such as (E)-alkenyl halides, (E)-α,β-unsaturated ketones or arylene-(E)-vinylene derivatives which are widely applied as fine chemicals, functional materials or building blocks in organic synthesis.
34 citations
TL;DR: A novel selective route to 1,1-bis(silyl)-1-alkenes has been developed by efficiently coupled in the presence of silver nitrate and palladium acetate with aryl or alkenyl idodides to give the corresponding silylative coupling exo-cyclization.
Abstract: A novel selective route to 1,1-bis(silyl)-1-alkenes has been developed. Sequential one-pot silylative coupling exo-cyclization of 1,2-bis(dimethylvinylsiloxy)ethane followed by the reaction with Grignard reagents leads to the desired 1,1-bis(silyl)ethenes, which are then efficiently coupled in the presence of silver nitrate and palladium acetate with aryl or alkenyl idodides to give the corresponding 1,1-bis(silyl)-2-arylethenes or 1,1,4-trisubstituted 1,3-butadienes with high yield.
33 citations
References
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280 citations
TL;DR: The Peterson-olefination reaction of equation (1) is used to prepare ketenedithio- 5, ketenediseleno acetals 8, trimethylsilyl- 11, 1,1-bis(trimethyl silyl)- 12, 1-alkylthio and 1-arylthio-1-stannyl olefins 19 from the α-silyllithium compounds 4, 7b, 9, 10, 15, and 18, respectively as discussed by the authors.
Abstract: Mit der Peterson-Olefinierungsreaktion der Gl. (1) werden aus den α-Silyllithium-Verbindungen 4, 7b, 9, 10, 15 und 18 Ketendithio- 5 bzw. Ketendiselenoacetale 8, Trimethylsilyl- 11, 1,1-Bis(trimethylsilyl)- 12, 1-Alkylthio- und 1-Arylthio-1-silyl- 16, sowie 1-Alkylthio- und 1-Arylthio-1-stannylolefine 19 hergestellt. Fur die Olefinierungsreagentien 7b, 9, 10, 15 und 18 werden neue oder verbesserte, ergiebige Erzeugungsmethoden beschrieben. Die Grenzen der Anwendbarkeit der Olefinierungsreaktionen werden diskutiert.
Generation of and Olefination with α-S-, -Se-, -Si-, and -Sn-perheterosubstituted (Trimethylsilyl)-methyllithium Derivatives
The Peterson-olefination reaction of equation (1) is used to prepare ketenedithio- 5, ketenediseleno acetals 8, trimethylsilyl- 11, 1,1-bis(trimethylsilyl)- 12, 1-alkylthio- and 1-arylthio-1-silyl- 16, as well as 1-alkylthio- and 1-arylthio-1-stannyl olefins 19 from the α-silyllithium compounds 4, 7b, 9, 10, 15, and 18, respectively. New or improved productive methods of generation of these olefinating reagents are described. The scope and limitations of the present olefinations are discussed.
156 citations
TL;DR: In this paper, the mechanism of this reaction has been elucidated based on reactions of 1 with vinylsilanes as well as those of the resulting ruthenium-silyl complex with alkenes.
Abstract: Selective cross-disproportion between vinylsilanes and various mono-substituted alkenes is catalysed by [RuCl(CO)H(PPh3)3]1; the mechanism of this reaction has been elucidated based on reactions of 1 with vinylsilanes as well as those of the resulting ruthenium–silyl complex with alkenes.
100 citations
TL;DR: The coupling reaction of styrene with vinylsilanes catalyzed by ruthenium complexes was investigated in this article, where RuHCl(CO) and RuCl(SiR3)(CO)(PPh3)2 were found to be efficient and selective catalysts for the formation of E-1-phenyl-2-silylethene and evolution of ethene.
89 citations