Direct Electrophilic Silylation of Terminal Alkynes

Andreev, A. A.; Коншин, В. В.; Комаров, Н. В.; Rubin, Michael; Brouwer, Chad; Gevorgyan, Vladimir

doi:10.1021/ol036328p

Cited by 41 publications

(20 citation statements)

References 25 publications

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“…Substituted alkynylsilanes are commonly used as alkynylating agents in the synthesis of organic and natural products11 as well as precursors of optoelectronic materials 12. They can be prepared by classical stoichiometric routes from organometallic reagents and, more recently, by metal‐complex‐catalyzed silylation of terminal alkynes with aminosilanes13a and chlorosilanes,13b dehydrogenative silylation with hydrosilanes,13c or other transformations of silyl‐substituted alkynes 13d. These reactions have been reviewed recently 14…”

Section: Methodsmentioning

confidence: 99%

A New Catalytic Route for the Activation of sp‐Hybridized Carbon–Hydrogen Bonds

Marciniec¹,

Dudziec²,

Kownacki³

2006

Angew Chem Int Ed

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In the last two decades we have developed a new type of transition-metal (TM)-catalyzed reaction of vinyl-substituted organosilicon compounds with olefins, known as a silylative coupling (SC, or trans-silylation; Scheme 1), that is complementary to metathesis. This reaction occurs by cleavage of the = C À H bond of an olefin and the = C À Si bond of a vinylsilane, in contrast to cross-metathesis, which uses the same substrates and also gives the same products (except the gem-isomer), by cleavage of the C=C bond. Various TM complexes (i.e. Ru, Rh, Ir, and Co) containing an MÀH and MÀSi bond initially, or one generated in situ, catalyze this process. [1,2] ) The mechanism for SC catalyzed by ruthenium complexes elucidated by Wakatsuki [3] and by us [4] involves insertion of a vinylsilane into the MÀH bond and b-Si transfer to the metal, with elimination of ethylene, to generate MÀSi species, then insertion of the alkene into the MÀSi bond and b-H transfer to the metal, with elimination of a substituted vinylsilane as product, and regeneration of the catalyst.The SC process under optimum conditions has become an excellent synthetic tool for the regio-and stereoselective synthesis of functionalized vinylsilicon compounds such as (E)-N-(silyl)vinylcarbazole, [5a] amides, [5b] 1-silyl-1-(boryl)-ethenes, [5c] functionalized cyclosiloxanes, cyclosilazanes, [5d] and silsesquioxanes [5e] as well as macromolecular organosilicon compounds containing (E)-1,2-bis(silyl)fragments. [6] These compounds can be used as synthetic reagents for organic synthesis and as materials precursors and are difficult to prepare by other TM-catalyzed reactions such as crossmetathesis. The trans-silylation reaction has recently been extended to other metalloids such as boron [7] and germanium.

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Section: Methodsmentioning

confidence: 99%

A New Catalytic Route for the Activation of sp‐Hybridized Carbon–Hydrogen Bonds

Marciniec¹,

Dudziec²,

Kownacki³

2006

Angew Chem Int Ed

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“…Alkynes with base‐ or nucleophile‐sensitive functional groups are also incompatible. Other approaches with X Si ,7 Me 2 N Si 8 or CH 2 CH Si 9 as silylating agents have emerged as well, but catalytic dehydrogenative silylation (D.S.) with hydrosilanes (H Si ) appears to be ideal for improving the above issues: reagent usability, atom‐economy, waste and functional group compatibility.…”

Section: Lewis Acid‐catalyzed Dehydrogenative Silylation Of 1‐octyne mentioning

confidence: 99%

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

et al. 2012

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“…Strategies for the synthesis of alkynylsilanes have employed strong bases (Scheme a, route A) or have relied on stoichiometric or catalytic transition metal species (Scheme a, Route B) and typically use various preactivated organosilicon coupling partners such as [Si–Cl], ,,, [Si–I], [Si–NR 2 ], [Si–Si], and [Si–OTf] . Inexpensive and convenient hydrosilanes have been investigated for C( sp )–H silylation; − ,,,,, however, the requisite in situ Si–H bond activation has thus far necessitated additional exogenous bases, , sacrificial hydrogen acceptors or external oxidants, , and elevated temperatures. − ,, Moreover, undesired hydrosilylation of the alkyne can be competitive, ,, further complicating catalyst and reaction design.…”

Section: Introductionmentioning

confidence: 99%

Alkali Metal-Hydroxide-Catalyzed C(sp)–H Bond silylation

et al. 2017

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Disclosed is a mild, scalable, and chemoselective catalytic cross-dehydrogenative C-H bond functionalization protocol for the construction of C(sp)-Si bonds in a single step. The scope of the alkyne and hydrosilane partners is substantial, providing an entry point into various organosilane building blocks and additionally enabling the discovery of a number of novel synthetic strategies. Remarkably, the optimal catalysts are NaOH and KOH.

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Direct Electrophilic Silylation of Terminal Alkynes

Cited by 41 publications

References 25 publications

A New Catalytic Route for the Activation of sp‐Hybridized Carbon–Hydrogen Bonds

A New Catalytic Route for the Activation of sp‐Hybridized Carbon–Hydrogen Bonds

Dehydrogenative Silylation of Terminal Alkynes with Hydrosilanes under Zinc–Pyridine Catalysis

Alkali Metal-Hydroxide-Catalyzed C(sp)–H Bond silylation

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