Hydrosilylation of CC and CC

Hiyama, Tamejiro; Kusumoto, Tetsuo

doi:10.1016/b978-0-08-052349-1.00245-6

Cited by 127 publications

(72 citation statements)

References 142 publications

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“…[50] Concerning the hydrosilylation reactions catalyzed by cyclopentadienylcobalt chelate 1, we believe that in the first step an oxidative addition of the hydrosilane with formation of complexes 2 takes place. According to the accepted mechanism of the hydrosilylation, [4,5,41,42] the decomplexation of the hemilable phosphane tether delivers a vacant coordination site, which is occupied by the alkyne. Insertion of the alkyne into the Co À Si or into the Co À H bond followed by reductive elimination accounts for product formation and catalyst regeneration.…”

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“…The distribution of the products is found to vary considerably with the nature of the catalyst, substrate and reaction conditions. [4,5,16] Significant progress has been achieved in recent years, and hydrosilylation reactions of terminal alkynes with high 1,2-syn, [9,17 -19] 1,2-anti, [20 -23] and 2,1 addition [24 -27] selectivity were reported successively.…”

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“…[3] Among the possible routes to alkenylsilanes, the most atom-economical and straightforward method is the transition metal-catalyzed hydrosilylation of alkynes. [4,5] The hydrosilylation of terminal alkynes to disubstituted alkenylsilanes has extensively been studied, and a variety of transition metal catalysts have been shown to be effective in this transformation. [6 -15] Generally the reaction results in a mixture of three different isomers, trans, cis, and a-isomers, as a result of 1,2-(syn-and anti-) and 2,1-additions, respectively (Scheme 1).…”

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Stereodivergent Formation of Alkenylsilanes: syn or anti Hydrosilylation of Alkynes Catalyzed by a Cyclopentadienylcobalt(I) Chelate Bearing a Pendant Phosphane Tether

Kirleis

Butenschön

2006

Adv Synth Catal

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Abstract:The hydrosilylation of alkynes is catalyzed by the di-tert-butylphosphanylethylcyclopentadienylcobalt chelate 1. While the reaction of internal alkynes exclusively affords syn hydrosilylation products with triethylsilane, the reaction with triethoxysilane shows predominant anti stereoselectivity. Reactions of terminal alkynes are less selective with triethylsilane and result in cyclotrimerization when triethoxysilane is used.

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Stereodivergent Formation of Alkenylsilanes: syn or anti Hydrosilylation of Alkynes Catalyzed by a Cyclopentadienylcobalt(I) Chelate Bearing a Pendant Phosphane Tether

Kirleis

Butenschön

2006

Adv Synth Catal

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“…We have examined the hydrosilylation of alkynes catalyzed by the ruthenium complex [Cp*Ru (MeCN) 3 ]PF 6 . Reactions catalyzed by this complex afford clean trans addition of a silane molecule to internal alkynes.…”

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Selective Synthesis of Functionalized Tertiary Silanes by Diastereoselective Rearrangement—Addition.

2006

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Treatment of hydroxy-substituted silyl-epoxides with Grignard reagents induces a 1,2-carbon shift to reveal α-silyl aldehydes, which are trapped by highly diastereoselective addition reactions of the Grignard reagent. The starting epoxides are readily accessible from propargylic alcohols by regioand diastereoselective hydrosilylation and epoxidation reactions. In addition to providing functionalized tertiary silane products, the method is shown to offer a tertiary olefin synthesis through chemo-and diastereoselective Peterson elimination of the product tertiary silane diols.Organosilicon compounds play an increasing role in organic synthesis wherein the silyl group serves as a sterically demanding directing group, 1,2 as a placeholder for oxygenation though Tamao-Fleming oxidation, 3 as an organometallic species for transition-metal catalyzed reaction, 4 or as a temporary, "traceless" tether for intramolecular reactions. 5 Additionally, allylic silanes are mild, stable nucleophiles. 2 However, in many respects methodology for the incorporation of silicon into complex targets lags behind the utility of such products. Most traditionally, reactive organometallic species are trapped with silyl chlorides. However, this approach negates the benefits of functional-group tolerance available to organosilicon-based routes. In addition, the generation of reactive organometallics such as Grignard reagents may be impossible in a congested, densely functionalized target. Other important routes, such as hydrosilylation, can be robust methods for primary alkyl 6 and vinylsilanes. 6,7 However, they are not generally compatible with the synthesis of highly congested silanes.We have examined the hydrosilylation of alkynes catalyzed by the ruthenium complex [Cp*Ru (MeCN) 3 ]PF 6 . Reactions catalyzed by this complex afford clean trans addition of a silane molecule to internal alkynes. A productive use of this method has been the hydrosilylation of propargylic alcohols, where (Z)-β-silyl allylic alcohols are formed selectively. 8 The placement of the silyl group offers the opportunity for diastereoselective epoxidation of the vinylsilane, 9 which can be further elaborated through silane oxidation (Scheme 1).We are interested in investigating other methods for the elaboration of the silylepoxide scaffold. Since allylic epoxides in general have a robust chemistry of selective ring-opening reactions, 10 we examined the possibility of selectively adding nucleophiles to silylepoxide 3 to afford bmtrost@stanford.edu.

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“…33 Na ausência de catalisadores, esta reação ocorre a altas temperaturas e pressões, mas geralmente emprega-se catálise fotoquímica, por peróxidos, por aminas terciárias ou por metais de transição para favorecer a reação. 34 O mecanismo da hidrosililação varia de acordo com alguns fatores, como solvente e temperatura de reação, mas irá depender principalmente do tipo de catálise empregada. …”

Section: 5) Hidrosililaçãounclassified

Estudos sobre a hidroteluração de álcoois propargílicos

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Hydrosilylation of CC and CC

Cited by 127 publications

References 142 publications

Stereodivergent Formation of Alkenylsilanes: syn or anti Hydrosilylation of Alkynes Catalyzed by a Cyclopentadienylcobalt(I) Chelate Bearing a Pendant Phosphane Tether

Stereodivergent Formation of Alkenylsilanes: syn or anti Hydrosilylation of Alkynes Catalyzed by a Cyclopentadienylcobalt(I) Chelate Bearing a Pendant Phosphane Tether

Selective Synthesis of Functionalized Tertiary Silanes by Diastereoselective Rearrangement—Addition.

Estudos sobre a hidroteluração de álcoois propargílicos

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