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

Organocatalytic enantioselective construction of Si-stereocenters: recent advances and perspectives DOI

Zhong-Tian Ye,

Zhongwei Wu,

Xue‐Xin Zhang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(17), P. 8546 - 8562

Published: Jan. 1, 2024

Silicon-stereogenic chiral organosilanes have found increasing applications in synthetic chemistry, medicinal and materials science. In this context, various asymmetric catalytic methods been established for the diverse synthesis of silicon-stereogenic silanes. particular, organocatalysis is emerging as an important complementary tool enantioselective construction silicon-stereocenters, along with rapid development chiral-metal catalyzed protocols. Its advent provides a powerful platform to achieve functionalized structural diversity, should lead great organosilicon chemistry. Tutorial Review, we highlight these latest achievements from two aspects: desymmetrizations prochiral tetraorganosilanes dynamic kinetic transformations racemic by employing five organocatalytic activation modes. The advantages, limitations value each protocol, well opportunities still open further exploration, are also discussed.

Language: Английский

Citations

13
Precision single-atom editing: new frontiers in nitrogen insertion and substitution for the generation of N-heterocycles DOI
Xue Li, Jia Xu, Zhigang Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4041 - 4053

Published: Jan. 1, 2024

This paper primarily focuses on the editing of nitrogen atoms, encompassing insertion N, substitution C with and utilization 15 N in place 14 for construction N-heterocycles.

Language: Английский

Citations

10
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 International Edition, Journal Year: 2024, Volume and Issue: 63(16)

Published: Feb. 23, 2024

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

9
Lewis Base-Catalyzed Dynamic Kinetic Asymmetric Transformation of Racemic Chlorosilanes en Route to Si-Stereogenic Silylethers DOI

Tianbao Hu,

Yan Zhang,

Wanshu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(33), P. 23092 - 23102

Published: Aug. 7, 2024

Enantiopure Si-stereogenic organosilanes are highly valued in the fields of organic synthesis, development advanced materials, and drug discovery. However, they not naturally occurring, their synthesis has been largely confined to resolution racemic silanes or desymmetrization symmetric silanes. In contrast, dynamic kinetic asymmetric transformation (DYKAT) offers a mechanistically distinct approach would broaden accessibility an enantioconvergent manner. this study, we report Lewis base-catalyzed DYKAT chlorosilanes. The chiral isothiourea catalyst, (S)-benzotetramisole, facilitates silyletherification with phenols, yielding (R)-silylethers good yields high enantioselectivity (27 examples, up 86% yield, 98:2 er). Kinetic analysis, control experiments, DFT calculations suggest that two-catalyst-bound pentacoordinate silicate is responsible for Si-configurational epimerization ion-paired tetracoordinated silicon intermediates.

Language: Английский

Citations

9
State-of-the-Art Advances in Enantioselective Transition-Metal-Mediated Reactions of Silacyclobutanes DOI
Li‐Wen Xu, Wei‐Sheng Huang, Qing Wang

et al.

Synthesis, Journal Year: 2022, Volume and Issue: 54(24), P. 5400 - 5408

Published: Aug. 23, 2022

Abstract Studies on the enantioselective transformation of silacyclobutanes (SCBs) have become an emerging topic in recent decade, due to feature high ring strain, and manageable Si–C bond cleavage formation. This short review summarizes remarkable achievements asymmetric transition-metal-mediated reaction benzosilacyclobutanes, resulting carbon- or silicon-stereogenic organosilanes with functional substituents. 1 Introduction2 Asymmetric Transition-Metal-Catalyzed Ring Expansion Reaction3 Ring-Opening Reaction4 Conclusion Outlook

Language: Английский

Citations

38
Synthesis of Alkynylsilanes: A Review of the State of the Art DOI
Krzysztof Kuciński

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(11), P. 2382 - 2431

Published: April 12, 2024

Abstract This contribution offers a comprehensive overview of methods for forging sp C−Si bonds. Over time, alkynylsilanes (silylacetylenes), once considered mere byproducts hydrosilylation processes, have become essential building blocks in organic synthesis. literature review traces the evolution their synthesis, from traditional methodologies relying on organolithium and organomagnesium compounds to more advanced cross‐coupling reactions involving hydro‐ carbosilanes. Focused primarily past 25 years (2000–2024), it also extensively references significant historical breakthroughs. By analyzing synthetic methodologies, not only survey current state knowledge but identifies areas improvement. Furthermore, emphasize importance 1‐alkynylsilanes (1‐silyl‐1‐alkynes), selected applications these are highlighted, confirming potential

Language: Английский

Citations

6
Tunable Regiodivergent Reactivity of N-Allenamides with Silacyclobutanes via Palladium Catalysis in the Synthesis of Silacyclic β-Aminosilanes DOI
Yidong Wang, Yan Sun, Tianying Liu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 10882 - 10892

Published: July 4, 2024

The key structure of β-aminosilanes has attracted significant interest because their latent biological activities in the field medicinal chemistry. However, structural variety been significantly constrained by absence a comprehensive synthetic approach. Thus, development regiodivergent catalytic systems for construction structurally diverse via an intermolecular cycloaddition strategy would represent addition to limited toolkit available synthesis. We herein present attractive approach synthesis through regioselective N-allenamides with expansion silacyclobutanes catalyzed Pd/PR3. Just selecting suitable protecting group N-allenamides, regioselectivity is completely switched efficiently provide two regioisomers silacyclic β-aminosilanes. Two regioselectivities were proceeded during migratory insertion and reductive elimination process, origin which could be well rationalized using density functional theory calculations.

Language: Английский

Citations

6
Recent Advances in Transition Metal-Catalyzed C—Si Bond Cleavage of Silacyclobutanes DOI Open Access
Min Liu, Liping Qi, Dongbing Zhao

et al.

Chinese Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 43(10), P. 3508 - 3508

Published: Jan. 1, 2023

Due to the widespread application of various organosilicon compounds in material science, electronic devices and pharmaceutical research, it is great significance develop green efficient synthetic methods for diverse silicon-containing molecules.Silacyclobutane an important kind small-membered rings, which exhibits unique reactivities under transition metal catalysis cleave C-Si bond driven by inherent ring strain Lewis acidity.The resulting Si-M species can then be transformed into compounds.Herein, recent advances Pd, Rh, Ni-catalyzed cleavage reactions silacyclobutanes are summarized detail, mechanism development tendency such briefly discussed.

Language: Английский

Citations

16
Photocatalyzed Thiosulfonylation of Sila-enynes with Thiosulfonates DOI
Zheng Tan, Fengjuan Chen, Guojin Huang

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(16), P. 2846 - 2851

Published: April 14, 2023

A photocatalyzed coupling-cyclization of sila-enynes with thiosulfonates has been developed. This reaction provides an efficient strategy to assemble thiosulfone-bifunctionalized benzosilacycles via sequential radical addition and coupling.

Language: Английский

Citations

13
Nickel(0)-catalyzed ring-opening reaction of silacyclobutanes with 1,3-dienes to access allylsilane DOI
Mengyuan Liu,

Kexin Dong,

Bing Xu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 3821 - 3826

Published: Jan. 1, 2024

Here we report a Ni-catalyzed highly regio- and stereoselective ring opening reaction of SCBs with 1,3-dienes for straightforward facile preparation allylsilanes.

Language: Английский

Citations

4