Tandem Synthesis of Linear Hydridopolycarbosilanes and Postfunctionalization by a Calcium Catalyst DOI
Lanxiao Zhao, Peng Deng, Xun Gong

et al.

Macromolecules, Journal Year: 2023, Volume and Issue: 56(23), P. 9550 - 9558

Published: Nov. 24, 2023

Recent years have witnessed great progress in the application of calcium-based catalysts a variety organic transformations, including hydrofuctionalization, dehydrogenative coupling, and C–H activation. However, these efficient protocols polymer synthesis remain much less explored. Here, we report selective bis-hydrosilylation dienes with bis-hydrosilanes presence scorpionate-supported calcium benzyl complex [(TpAd,iPr)Ca(p-CH2–C6H4-Me)(THP)] (TpAd,iPr = hydrotris(3-adamantyl-5-isopropyl-pyrazolyl)borate, THP tetrahydropyran) (1) to obtain linear polycarbosilanes containing reactive SiH2 unit main chain. Furthermore, 1 can also catalyze silylation terminal alkyne, silylamination aniline, activation 1-methyl-1H-indole, Si–H bonds allow introduction 35–65% new side chains polymers. The resulting polymers contain unusual units SiH–(C≡CPh), SiH–(NHAr), SiH–(indole), whose is confirmed by NMR IR spectra.

Language: Английский

Catalytic asymmetric synthesis of silicon-stereogenic organosilanes DOI Creative Commons
Yichen Wu,

Long Zheng,

Yan Wang

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3461 - 3514

Published: Oct. 19, 2023

Language: Английский

Citations

35
Chiral PSiSi‐Ligand Enabled Iridium‐Catalyzed Atroposelective Intermolecular C−H Silylation DOI
Bo Yang,

Jihui Gao,

Xing-Fa Tan

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(36)

Published: July 18, 2023

Catalytic enantioselective intermolecular C-H silylation offers an efficient approach for the rapid construction of chiral organosilicon compounds, but remains a significant challenge. Herein, new type silyl ligand is developed, which enables first iridium-catalyzed atroposelective reaction 2-arylisoquinolines. This protocol features mild conditions, high atom economy, and remarkable yield with excellent stereoselectivity (up to 99 % yield, ee), delivering enantioenriched axially silane platform molecules facile convertibility. Key success this unprecedented transformation relies on novel PSiSi-ligand, facilitates process perfect chem-, regio- stereo-control via multi-coordinated iridium complex.

Language: Английский

Citations

28
Catalytic Kinetic Resolution of Monohydrosilanes via Rhodium‐Catalyzed Enantioselective Intramolecular Hydrosilylation DOI

Fei‐Hu Gou,

Fei Ren, Yichen Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(25)

Published: April 12, 2024

The catalytic access of silicon-stereogenic organosilanes remains a big challenge, and largely depends on the desymmetrization symmetric precursors with two identical substitutes attached to silicon atom. Here we report construction via kinetic resolution racemic monohydrosilanes good excellent selectivity factors. Both Si-stereogenic dihydrobenzosiloles could be efficiently accessed in one single operation Rh-catalyzed enantioselective intramolecular hydrosilylation, employing (R,R)-Et-DuPhos as optimal ligand. This protocol features mild conditions, low catalyst loading (0.1 mol % [Rh(cod)Cl]

Language: Английский

Citations

13
The role of silicon in drug discovery: a review DOI Creative Commons
Jenny‐Lee Panayides, Darren L. Riley, Felix Hasenmaile

et al.

RSC Medicinal Chemistry, Journal Year: 2024, Volume and Issue: 15(10), P. 3286 - 3344

Published: Jan. 1, 2024

This review aims to highlight the role of silicon in drug discovery.

Language: Английский

Citations

13
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
Catalytic Asymmetric Construction of C‐ and Si‐Stereogenic Silacyclopentanes via Hydrosilylation of Arylmethylenecyclopropanes DOI

Liexin Wu,

Lu Zhang, Jiandong Guo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Aug. 14, 2024

Silacycles have exhibited significant potential for application in the fields of medicinal chemistry, agrochemistry, and materials science. Accordingly, development effective methods synthesizing these compounds has attracted increasing attention. Here, we report an efficient Cu-catalyzed enantioselective hydrosilylation arylmethylenecyclopropanes with hydrosilanes, that allows rapid assembly various enantioenriched carbon- silicon-stereogenic silacyclopentanes good yields excellent enantioselectivities diastereoselectivities under mild conditions. Further stereospecific transformation Si-H bond on chiral silicon center expands diversity C- Si-stereogenic silacyclopentanes.

Language: Английский

Citations

12
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

11
Nickel(0)-Catalyzed Stereospecific and Enantioselective Ring-Opening Hydrosilylation of Methylenecyclopropanes to Access (E)-Homoallylsilanes DOI
Ji Zhang, Jiawei Guo, Wanlin Liu

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3126 - 3133

Published: Feb. 6, 2025

Language: Английский

Citations

2
Catalytic Asymmetric Dehydrogenative Si–H/X–H Coupling toward Si-Stereogenic Silanes DOI

Yicong Ge,

Jie Ke, Chuan He

et al.

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be topic of high current relevance modern organic chemistry, given their versatile utility as chiral building blocks, reagents, auxiliaries, catalysts. Historically, access these non-natural silanes mainly relies on resolution, whereas asymmetric synthetic methods dramatically lagged compared carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization prochiral organosilanes has emerged an effective tool for synthesis enantioenriched silanes. Despite progress, catalytic reactions usually suffer from limited substrate scope, poor functional-group tolerance, low enantioselectivity. The growing demand with structural diversity continued drive development new practical assembly molecules.Five years ago, our research group embarked project aimed at developing general approach that can unlock functionalized efficiency. This Account describes laboratory's endeavor exploration dehydrogenative Si–H/X–H coupling toward features (1) readily accessible dihydrosilane starting materials; (2) diverse X–H (X═C, N, O, etc.) partners; (3) platform transformable monohydrosilane products; (4) efficiency atomic economy.At initial stage research, biaryl was selected model conduct enantioselective intramolecular C–H/Si–H reaction. Rh/Josiphos system found early this process, while final enantiocontrol elusive. Mechanistic studies indicated rhodium silyl dihydride complex is resting state cycle, which may undergo racemization center. Enlightened by mechanistic investigations, strategies, tandem alkene hydrosilylation strategy bulky alkene-assisted strategy, were adopted avoid racemization, delivering corresponding 9-silafluorenes excellent yields enantioselectivities. Further C(sp2)–H or C(sp3)–H silylation gave series five-, six- seven-membered heterocycles Next, we extended reaction intermolecular version, realizing Si–H/C–H, Si–H/O–H, Si–H/N–H variety acyclic monohydrosilanes, ethers, siloxanes, silanols, silazanes. We also presented endeavors apply resulting compounds, including further derivatization, polymerization, chiroptical property successfully introduced Si-stereocenters into bioactive molecules, polymers, materials. Lastly, based understanding metal species, developed type ligand applied enable atroposelective anticipate methodology, insights, studies, will not only inspire chemistry but contribute creation novel molecules medicinal materials science.

Language: Английский

Citations

1
Recyclable Iridium Catalyst Supported on Porous Organic Polymer for Acceptorless Dehydrogenative Silylation: Synthesis of Ring‐Fused Oxasilacycles DOI

Jiayi Xian,

Xing Sheng,

Yi Lin

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(8), P. 1763 - 1769

Published: March 1, 2024

Abstract The direct conversion of specific C−H bonds to C−Si in alkanes or aromatics via catalytic methods has attracted growing research interest. Herein, we report the preparation a new iridium catalyst supported on naphthyridine‐based porous organic polymer and its successful application dehydrogenative silylation 2‐arylphenols alcohol hydrosilanes access ring‐fused oxasilacycles. synthetic method exhibits broad substrate scope good functional group compatibility while avoiding use hydrogen acceptors. In addition, this could be easily recovered from reaction system reused for at least seven times without apparent deactivation. This provides insights further design heterogeneous nanocatalysts contributes synthesis silicon‐substituted molecules.

Language: Английский

Citations

6