Pyrolysis of 1-(trimethylsilyl)-1-alkanols. New carbene precursors of silylcarbene and phenylcarbene

Sekiguchi, Akira; Andō, Wataru

doi:10.1021/jo01314a012

Cited by 11 publications

(1 citation statement)

References 3 publications

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“…Detailed studies of (trimethylsilyl)(carboethoxy)carbene (67), (trimethylsilyl)-phenylcarbene (68), (trimethylsilyl)carbene (69), and bis(trimethylsilyl)carbene (70) have also been reported. The pyrolysis of 1-(trimethylsilyl)-l-alkanols (such as 66) as a method of carbene formation holds considerable promise (71).…”

Section: Carbenoid Chemistrymentioning

confidence: 99%

Silicon-Mediated Organic Synthesis

Paquette

1982

Science

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Organic chemists have used the chemical properties of tetracovalent silicon in a remarkable variety of new synthetic transformations. In carbon-functional silanes, exceptional stabilization is provided to a carbocation center in the beta position when the carbon-silicon bond lies in plane. This phenomenon directs electrophilic attack to the silicon-substituted carbon in aryl-, vinyl-, and alkynylsilanes and to carbon-3 in allylsilanes. For different reasons, silicon also stabilizes a carbon-metal bond in the alpha position. Consequently, access to many silicon-containing organometallics is readily available. The exceptional strength of silicon-oxygen and silicon-fluorine bonds is yet another factor that controls the chemical reactivity of silicon reagents. In recent developments, preparative chemists have taken advantage of these properties in imaginative and useful ways.

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Section: Carbenoid Chemistrymentioning

confidence: 99%

Silicon-Mediated Organic Synthesis

Paquette

1982

Science

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Silicon‐Substituted Carbenes

Maas

2009

Patai's Chemistry of Functional Groups

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Synthesizing Silyl Arylsulfonyl Hydrazones as Silyldiazomethane Precursors and Their Use in Rhodium‐Catalyzed Reactions

Tsuruda,

Saito,

Matsuzaki

et al. 2024

Adv Synth Catal

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A method for synthesizing silyl arylsulfonyl hydrazones as silyldiazomethane precursors has been developed. Although silyldiazomethanes are an important class of diazo compounds, their use in intramolecular cyclization reactions has not been fully explored despite the rich chemistry of diazo compounds, particularly metal carbenoid chemistry. The fundamental challenge underlying the absence of such studies is the lack of a method for synthesizing silyldiazomethanes with functional groups that can react with metal carbenoids. The method reported here provides access to variety of silyl arylsulfonyl hydrazones with functional groups such as ethers, carbamates, and alkynes, which can serve as reaction sites for metal carbenoids. A one‐pot hydrazone formation using unstable formylsilane formed in situ is key to a successful synthesis. The use of 2,4,6‐trimethylbenzenesulfonohydrazide contributed toward achieving broad generality in hydrazone formation. The synthetic potential of this method was demonstrated through the generation of silyldiazomethane and its transformation to several silacycles.

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Pyrolysis of 1-(trimethylsilyl)-1-alkanols. New carbene precursors of silylcarbene and phenylcarbene

Cited by 11 publications

References 3 publications

Silicon-Mediated Organic Synthesis

Silicon-Mediated Organic Synthesis

Silicon‐Substituted Carbenes

Synthesizing Silyl Arylsulfonyl Hydrazones as Silyldiazomethane Precursors and Their Use in Rhodium‐Catalyzed Reactions

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