Rhodium-Catalyzed Addition of (Trialkylsilyl)arenes to Electrophiles via π-Coordination-Driven C–Si Bond Activation DOI
Yunzhi Lin,

Hang Shi

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(41), P. 22753 - 22761

Published: Oct. 3, 2023

Aromatic organosilicon compounds serve as valuable synthons due to their diverse reactivities, excellent compatibility with various functional groups, and ready availability. However, (trialkylsilyl)arenes, despite potential utility, are generally considered unsuitable substrates for transition-metal-catalyzed cross-coupling the low polarity of covalent C(aryl)-Si bonds significant steric hindrance imposed by alkyl substituents. These factors render them inert toward reactions transition metals, such transmetalation oxidative addition. In this study, we present a method rhodium-catalyzed addition (trialkylsilyl)arenes electrophiles via π-coordination-driven desilylation. We propose that dicationic rhodium species activates unbiased bond, increasing its forming an η6-arene complex, thereby facilitating heterolysis. The resulting phenyl anion complex readily engages in external electrophiles, effectively C-C bonds. Through comprehensive computational studies, have unraveled unexpected stepwise pathway desilylation fluoride. This involves fluoride aromatic ring, followed 1,2-migration fluoride, ultimately culminating departure fluorotrimethylsilane.

Language: Английский

Photocatalytic site-selective radical C(sp3)–H aminoalkylation, alkylation and arylation of silanes DOI

Xingyi He,

Yizhi Zhang, Shanshan Liu

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 10, 2024

Language: Английский

Citations

4
Palladium-catalyzed addition of acylsilanes across alkynes via the activation of a C–Si bond DOI Creative Commons

Tetsuya Inagaki,

Takahiro Ando,

Shun Sakurai

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(10), P. 2706 - 2712

Published: Jan. 1, 2023

Palladium-catalyzed addition of a C–Si bond in acylsilanes across the triple bonds an alkyne bearing carbonyl group at one terminal is reported.

Language: Английский

Citations

10
Rhodium-Catalyzed Hydrolytic Cleavage of the Silicon–Carbon Bond of Silacyclobutanes to Access Silanols DOI

Wei-Ke Zhu,

Hua‐Jie Zhu,

Xiao‐Jun Fang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(39), P. 7186 - 7191

Published: Sept. 27, 2023

Herein, we report the first rhodium-catalyzed hydrolytic cleavage of silicon–carbon bond in silacyclobutanes using water as reactant. A series could be employed this reaction presence Rh/BINAP complex, resulting corresponding silanols good yields. Additionally, a chiral 1,1,4,4-tetraaryl-2,3-O-isopropylidene-l-threitol-derived phosphoramidite ligand used to yield Si-stereogenic silanol with promising enantioselectivity.

Language: Английский

Citations

10
Enantioselective construction of silicon-stereogenic vinylsilanes from simple alkenes DOI Creative Commons

Kailin Yin,

Ji Zhang, Deng Pan

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: Jan. 18, 2025

The diverse utility of acyclic vinylsilanes has driven the interest in synthesis enantioenriched bearing a Si-stereogenic center. However, predominant approaches for catalytic asymmetric generation have mainly relied on transition metal-catalyzed reactions alkynes with different silicon sources. Here we successfully realize enantioselective linear silicon-stereogenic good yields and enantiomeric ratios from simple alkenes under rhodium catalysis. significance this transformation lies its ability to achieve regioconvergent enantioconvergent conversion, efficiently transforming petroleum-derived isomeric mixtures olefin feedstocks into single regio- stereoisomer product. practicality method is further exemplified by downstream transformations these leveraging functionality leaving group nature aryl substituent as well development chiral π-conjugated double bond systems.

Language: Английский

Citations

0
The literature of heterocyclic chemistry, part XXII, 2022 DOI
Галина А. Газиева, Yu. B. Evdokimenkova, N. O. Soboleva

et al.

Advances in heterocyclic chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Language: Английский

Citations

0
Recent Progress in the Construction of Silacycles by Transition- Metal-Catalyzed C—H Silylation DOI
Ze‐Shui Liu, Zhenzhen Guo, Jun‐Long Niu

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 423 - 423

Published: Jan. 1, 2025

Language: Английский

Citations

0
Photo-induced ring-maintaining hydrosilylation of unactivated alkenes with hydrosilacyclobutanes DOI Creative Commons
Shaowei Chen,

Meiyun Gao,

Xiaoqian He

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 12, 2025

Abstract Increasing attention has been paid to silacyclobutanes because of their wide application in ring opening and extension reactions. However, the synthesis functionalized remains an unmet challenge limited functional group tolerance reactions with organometallic reagents chlorosilacyclobutanes. Herein, we report a conceptually different solution this end through visible-light-induced metal-free hydrosilylation unactivated alkenes hydrosilacyclobutanes. A range diverse groups including base-sensitive acid, alcohol ketones participated reaction smoothly. In particular, first dihydrosilacyclobutane provides facile access various alkyl monohydrosilacyclobutanes. Unsymmetrical dialkyl have also synthesized consecutive one pot. The mechanism study reveals that Lewis basic solvent could promote generation strained silyl radicals by direct light irradiation without redox-active photocatalyst thiol catalyst plays important role accelerating reaction.

Language: Английский

Citations

0
Enantioselective synthesis of silicon-stereogenic siladihydrofuran via copper-catalyzed Si-C bond cleavage DOI

Chang Su,

Yidong Wu, Pan‐Pan Chen

et al.

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 116089 - 116089

Published: March 1, 2025

Language: Английский

Citations

0
Modular and Regioselective Synthesis of Eight-Membered Benzosilacycles Enabled by Ring Expansion of Silacyclobutanes with Aryl Halides and Alkynes DOI
Zhenzhen Guo, Jinxiang Ye, Yingying Zhang

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7066 - 7078

Published: April 16, 2025

Language: Английский

Citations

0
Ring Expansion toward Disila‐carbocycles via Highly Selective C−Si/C−Si Bond Cross‐Exchange DOI
Min Liu,

Nuo Yan,

Haowen Tian

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(16)

Published: Feb. 23, 2024

Abstract Herein, we successfully inhibited the preferential homodimerization and C−Si/Si−H bond cross‐exchange of benzosilacyclobutenes monohydro‐silacyclobutanes achieved first highly selective C−Si/C−Si reaction by deliberately tuning Ni‐catalytic system, which constitutes a powerful atom‐economical ring expansion method for preparing medium‐sized cyclic compounds bearing two silicon atoms at junction, are otherwise inaccessible. The DFT calculation explicitly elucidated pivotal role Si−H silacyclobutanes high strain substrates in realizing C−Si bonds cleavage reformation catalytic cycle.

Language: Английский

Citations

3