Versatile OPiv-Supported Organozinc Reagents for Transition-Metal-Catalyzed Cross-Couplings DOI
Jie Li, Xingchen Liu, Jixin Wang

et al.

Synlett, Journal Year: 2022, Volume and Issue: 33(17), P. 1688 - 1694

Published: June 9, 2022

Abstract As one of the most important indispensable tools, organozinc-reagents-based Negishi cross-couplings have been extensively utilized for synthesis biologically active molecules and feedstock commodity chemicals. However, use air- moisture-sensitive organozinc halides expensive palladium catalysis still remain drawbacks. Recently, user-friendly solid OPiv-supported C–Zn, Si–Zn reagents with enhanced air moisture stability prepared, which displayed superior reactivity in various transition-metal-catalyzed cross-couplings, especially earth-abundance cobalt nickel catalysis. Herein, we summarized recent advances our research work field preparation application pivalates present short review. 1 Introduction 2 Development Organozinc Pivalates Two-Component Cross-Couplings 3 Three-Component 4 Conclusion Outlook

Language: Английский

Organic Photoredox-Catalyzed Silyl Radical Generation from Silylboronate DOI

Naho Takemura,

Yuto Sumida, Hirohisa Ohmiya

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(13), P. 7804 - 7810

Published: June 16, 2022

A visible-light-driven silyl radical generation method from silylboronates has been developed. The activation of with a catalytic amount mild base promoted the single-electron oxidation process to form radicals. Facile single electron transfer for borate readily occurred without hydrogen atom hydrosilane in presence various photoredox catalysts. Combining this protocol radical-mediated N-heterocyclic carbene catalysis enabled acylsilylation alkenes via relay generation. Furthermore, recent advanced methods synthesis significantly improved utility process.

Language: Английский

Citations

77

Salt‐Stabilized Silylzinc Pivalates for Nickel‐Catalyzed Carbosilylation of Alkenes DOI
Jixin Wang,

Zhili Duan,

Xingchen Liu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(17)

Published: Feb. 18, 2022

Abstract We herein report the preparation of solid and salt‐stabilized silylzinc pivalates from corresponding silyllithium reagents via transmetalation with Zn(OPiv) 2 . These resulting organosilylzinc show enhanced air moisture stability unique reactivity in silylative difunctionalization alkenes. Thus, a practical chelation‐assisted nickel‐catalyzed regioselective alkyl benzylsilylation alkenes has been developed, which provides an easy method to access silanes broad substrate scope wide functional group compatibility. Kinetic experiments highlight that OPiv‐coordination is crucial improve pivalates. Furthermore, late‐stage functionalizations druglike molecules versatile modifications products illustrate synthetical utility this protocol.

Language: Английский

Citations

44

Nickel-Catalyzed Reductive [4 + 1] Sila-Cycloaddition of 1,3-Dienes with Dichlorosilanes DOI
Liangliang Qi,

Qiu‐Quan Pan,

Xiao‐Xue Wei

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(24), P. 13008 - 13014

Published: June 7, 2023

Transition-metal-catalyzed sila-cycloaddition has been a promising tool for accessing silacarbocycle derivatives, but the approach limited to selection of well-defined sila-synthons. Herein, we demonstrate potential chlorosilanes, which are industrial feedstock chemicals, this type reaction under reductive nickel catalysis. This work extends scope coupling from carbocycle synthesis and single C-Si bond formation reactions. The proceeds mild conditions shows good substrate functionality tolerance, it offers new access silacyclopent-3-enes spiro silacarbocycles. optical properties several dithienosiloles as well structural variations products demonstrated.

Language: Английский

Citations

34

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

11

Silylarylation of Alkenes via meta-Selective C–H Activation of Arenes under Ruthenium/Iron Cooperative Catalysis: Mechanistic Insights from Combined Experimental and Computational Studies DOI

Sukanya Neogi,

Sourav Bhunya,

Asim Kumar Ghosh

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(7), P. 4510 - 4522

Published: March 12, 2024

Organosilicons are privileged skeletons in the domains of pharmaceutical chemistry, organic synthesis, and materials science. Hence, investigating catalytic techniques for synthesis organosilicon compounds has received a great deal emphasis. Carbosilylation alkenes is an efficient technique to introduce diverse molecular architectures containing silicon into chemical space. However, organohalides pseudohalides prerequisites most existing carbosilylation protocols. On other hand, utilization C–H activation been sowing seeds successful development intricate scaffolds. In this regard, synthetic accessibility complexed derivatives by through meta-C–H approach remained intangible. Herein, we present three-component strategy arylsilylation olefins with (het)arenes silanes integrating iron-catalyzed silyl radical generation, coupled intrinsic reactivity alkene, ruthenium-catalyzed functionalization (het)arene, leading targeted cross-coupled carbosilylated product. addition, theoretical investigations state-of-the-art dispersion corrected density functional theory at B3PW91-D3/Def2TZVP/CPCM(PhCF3) shed intriguing insights on selectivity probable mechanistic pathway underexplored cooperative 3d/4d transition metal catalysis, such as formation its addition alkene catalyzed iron, followed meta-selective ruthenium bound arene, furnishing C4 substituted (het)arene functionalized compounds.

Language: Английский

Citations

10

Recent Advances in Mono‐ and Difunctionalization of Unactivated Olefins DOI

Monak Patel,

Bhargav Desai, Aakash Sheth

et al.

Asian Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 10(12), P. 3201 - 3232

Published: Nov. 5, 2021

Abstract Olefins are synthetically useful building blocks in modern organic synthesis. Direct functionalization of olefins; represent one the most explored transformations synthetic chemistry due to their easy availability and reactivity towards large number reactants affording diverse range compounds. In recent times, development new protocols for olefins is a growing realm. A plethora olefin methodologies have been reported literature through ionic free radical mechanisms including single electron transfer (SET) last two decades. This review gives an overview mono‐ difunctionalization unactivated olefins, with emphasis on mechanistic details.

Language: Английский

Citations

52

Nickel‐Catalyzed Cross‐Electrophile 1,2‐Silyl‐Arylation of 1,3‐Dienes with Chlorosilanes and Aryl Bromides DOI

Qiu‐Quan Pan,

Liangliang Qi,

Xiaobo Pang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(4)

Published: Nov. 26, 2022

Abstract Catalytic, three‐component, cross‐electrophile reactions have recently emerged as a promising tool for molecular diversification, but studies focused mainly on the alkyl‐carbonations of alkenes. Herein, scope this method has been extended to conjugated dienes and silicon chemistry through silylative difunctionalization 1,3‐dienes with chlorosilanes aryl bromides. The reaction proceeds under mild conditions afford 1,2‐linear‐silylated products, selectivity that is different those obtained from conventional methods via an intermediary H(C)‐η 3 ‐π‐allylmetal species. Preliminary mechanistic reveal chlorosilane reacts 1,3‐diene first then couples bromide.

Language: Английский

Citations

39

Nickel/photoredox-catalyzed three-component silylacylation of acrylates via chlorine photoelimination DOI Creative Commons

Yejin Koo,

Sungwoo Hong

Chemical Science, Journal Year: 2024, Volume and Issue: 15(20), P. 7707 - 7713

Published: Jan. 1, 2024

By leveraging the synergistic interplay between nickel and photoredox catalysis, we have developed a three-component silylacylation strategy for various acrylates, yielding valuable building blocks with carbonyl silicon functionalities.

Language: Английский

Citations

7

Light-Promoted Arylsilylation of Alkenes with Hydrosilanes DOI

Wanyao Zheng,

Yongjie Xu, Hang Luo

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(39), P. 7145 - 7150

Published: Sept. 22, 2022

Herein, we report light-promoted photo/hydrogen atom transfer dual catalysis for arylsilylation of alkenes via the radical-radical cross-coupling with diverse hydrosilanes, which provides a simple and efficient method to prepare various organosilicon compounds wide range substrate scope good functional group tolerance under transition-metal- chemical-oxidant-free conditions. Furthermore, can also proceed possible electron donor-acceptor complex exogenous photocatalyst-free

Language: Английский

Citations

29

Cationic-palladium catalyzed regio- and stereoselective syn-1,2-dicarbofunctionalization of unsymmetrical internal alkynes DOI Creative Commons
Shubham Dutta,

Shashank Shandilya,

Shengwen Yang

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: March 16, 2022

Abstract π-Extended tetrasubstituted olefins are widely found motifs in natural products, leading drugs, and agrochemicals. Thus, development of modular strategies for the synthesis complex all-carbon-substituted always draws attention. The difunctionalization unsymmetrical alkynes is an attractive approach but it has remained faced with regioselectivity issues. Here we report discovery a regio- stereoselective syn -1,2-dicarbofunctionalization internal alkynes. A cationic Pd-catalyzed three-component coupling aryl diazonium salts, boronic acids (or olefins) yne-acetates enables access to all-carbon substituted olefins. transformation features broad scope labile functional group tolerance, building chemical space structural diversity (94 molecules). value this synthetic method demonstrated by direct products drug candidates containing yne-acetates, enable highly structurally allyl acetate analogues biologically important compounds. Synthetic versatility carboxylate bearing also presented. reaction outcome attributed situ formation stabilized aryl-Pd species, which regulates regioselective aryl-palladation yne-acetates. Control experiments reveal synergy between protecting Pd-intermediate productivity; density theory (DFT) studies rationalize selectivity reaction.

Language: Английский

Citations

28