Recent advances in C–Si bond activation via a direct transition metal insertion

Fu, Pingqing; Zhang, Yuebao; L, Gao; Song, Zhenlei

doi:10.1016/j.tetlet.2015.01.184

Cited by 95 publications

(12 citation statements)

References 42 publications

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“…These results indicate that the cleavage of the Si−C(sp 3 ) bond by the bis(phosphine)palladium(0) catalyst is not so easy even for a silacyclobutane with ring strain, and it is not likely to happen without the aid of another substrate to modify the thermodynamics of the reaction. In this regard, the hypothesis that 1‐pallada‐2‐silacylopentanes may be intermediates in several palladium‐catalyzed C−Si bond‐cleavage reactions does not fit this reaction . These findings are consistent with the experimental fact that [Pd(PPh 3 ) 4 ] does not react with 1 a (Equation (2), Scheme ).…”

Section: Resultssupporting

confidence: 75%

“…In this regard, the hypothesis that 1-pallada-2-silacylopentanes may be intermediates in severalp alladium-catalyzedC ÀSi bond-cleavage reactions does not fit this reaction. [9][10][11] These findings are consistent with the experimental fact that [Pd(PPh 3 ) 4 ]d oes not react with 1a (Equation (2), Scheme 1). However, the oxidative addition of the monophosphine Pd 0 complex [Pd 0 PMe 3 ]t ot he SiÀCb ond leading to IA2 was found to proceed withoutany barriers.…”

Section: Catalytic Cycles Promoted By the Palladium/trialkylphosphinesupporting

confidence: 87%

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Palladium‐Catalyzed Desymmetrization of Silacyclobutanes with Alkynes to Silicon‐Stereogenic Silanes: A Density Functional Theory Study

Zhang

Zheng

et al. 2016

Chemistry An Asian Journal

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The palladium-catalyzed desymmetrization of silacyclobutanes using electron-deficient alkynes proceeds with high enantioselectivity in the presence of a chiral P ligand; this provides a facile approach for the synthesis of novel silicon-stereogenic silanes. In this work, we used hybrid density functional theory (DFT) to elucidate the mechanism of the palladium-catalyzed desymmetrization of silacyclobutanes with dimethyl acetylenedicarboxylate. Full catalytic cycle including two different initiation modes that were proposed to be a possible initial step to the formation of the 1-pallada-2-silacyclopentane/alkyne intermediate-the oxidative addition of the palladium complex to the silacyclobutane Si-C bond (cycle MA) or coordination of the Pd complex with the alkyne C≡C bond (cycle MB)-have been studied. It was found that the ring-expansion reaction began with cycle MB is energetically more favorable. The formation of a seven-membered metallocyclic Pd intermediate was found to be the rate-determining step, whereas the enantioselectivity-determining step, oxidative addition of silacyclobutane to the three-membered metallocyclic Pd intermediate, was found to be quite sensitive to the steric repulsion between the chiral ligand and silacyclobutane.

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Section: Resultssupporting

confidence: 75%

Section: Catalytic Cycles Promoted By the Palladium/trialkylphosphinesupporting

confidence: 87%

Palladium‐Catalyzed Desymmetrization of Silacyclobutanes with Alkynes to Silicon‐Stereogenic Silanes: A Density Functional Theory Study

Zhang

Zheng

et al. 2016

Chemistry An Asian Journal

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“…[19] The following three pathways were considered via the rare example of C(sp 2 )ÀSi bond cleavage in 4a:1 )substitutiono ft he aromatic rings of 4a through nucleophilic attack of the silicon center by the electron-rich anisyl ring [pathway (1)]; [20] 2) exchange of aryl groups by cleavage of CÀ Si bonds through oxidative addition of Rh I to the CÀSi bond of intermediate C,f ollowed by reductivee limination leadingt oD [pathway (2)], [21] which was proposed on the basis of the reporto fr hodium-catalyzed C(sp 2 )ÀSi bond cleavagel eading to benzosiloles by To bisu,C hatani et al [19b] Intermediate D was then converted to 4a' by s-complex-assisted metathesis (s-CAM); [22] and 3) cleavage of CÀSi bonds of spiro-9-silabifluorene 2a by an Rh I ÀHs pecies, which coordinates to the newly formed CÀSi s bond just after its formation [pathway (3)]. [23] The resultingi ntermediate E was then converted to 4a' by s-CAM. [22] Because these three pathwayss hould afford 4a' as ar acemic mixture, as the S form, and as the R form, respectively,t he change in the absolutec onfigurationo ft he product in the conversion of 4a was investigated.…”

Section: Resultsmentioning

confidence: 99%

Rhodium‐Catalyzed Synthesis of Chiral Spiro‐9‐silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters

Murai

Takeuchi

Yamauchi

et al. 2016

Chemistry A European J

110

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Mechanistic insight into the construction of quaternary silicon chiral centers by rhodium-catalyzed synthesis of spiro-9-silabifluorenes through dehydrogenative silylation is reported. The C2 -symmetric bisphosphine ligand, BINAP, was effective in controlling enantioselectivity, and axially chiral spiro-9-silabifluorenes were obtained in excellent yields with high enantiomeric excess. Monitoring of the reaction revealed the presence of a monohydrosilane intermediate as a mixture of two constitutional isomers. The reaction proceeded through two consecutive dehydrogenative silylations, and the absolute configuration was determined in the first silylative cyclization. Competitive reactions with electron-rich and electron-deficient dihydrosilanes indicated that the rate of silylative cyclization increased with decreasing electron density on the silicon atom of the starting dihydrosilane. Further investigation disclosed a rare interconversion between the two constitutional isomers of the monohydrosilane intermediate with retention of the absolute configuration.

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“…Since Kipping’s pioneering synthesis of octaphenylcyclotetrasilane, strained three- or four-membered silacycles − have remained some of the most active research areas for chemists over the past 100 years. These small-ring silacycles have been extensively studied in main-group chemistry and have found numerous applications in organic synthesis.…”

Section: Introductionmentioning

confidence: 99%

3-Silaazetidine: An Unexplored yet Versatile Organosilane Species for Ring Expansion toward Silaazacycles

Wang

Zhou

et al. 2021

J. Am. Chem. Soc.

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Small-ring silacycles are important organosilane species in main-group chemistry and have found numerous applications in organic synthesis. 3-Silaazetidine, a unique small silacycle bearing silicon and nitrogen atoms, has not been adequately explored due to the lack of a general synthetic scheme and its sensitivity to air. Here, we describe that 3-silaazetidine can be easily prepared in situ from diverse air-stable precursors (RSO2NHCH2SiR1 2CH2Cl). 3-Silaazetidine shows excellent functional group tolerance in a palladium-catalyzed ring expansion reaction with terminal alkynes, giving 3-silatetrahydropyridines and diverse silaazacycle derivatives, which are promising ring frameworks for the discovery of Si-containing functional molecules.

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Recent advances in C–Si bond activation via a direct transition metal insertion

Cited by 95 publications

References 42 publications

Palladium‐Catalyzed Desymmetrization of Silacyclobutanes with Alkynes to Silicon‐Stereogenic Silanes: A Density Functional Theory Study

Palladium‐Catalyzed Desymmetrization of Silacyclobutanes with Alkynes to Silicon‐Stereogenic Silanes: A Density Functional Theory Study

Rhodium‐Catalyzed Synthesis of Chiral Spiro‐9‐silabifluorenes by Dehydrogenative Silylation: Mechanistic Insights into the Construction of Tetraorganosilicon Stereocenters

3-Silaazetidine: An Unexplored yet Versatile Organosilane Species for Ring Expansion toward Silaazacycles

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