Photoredox Metal-Free Allylic Defluorinative Silylation of α-Trifluoromethylstyrenes with Hydrosilanes

Review Chemistry, Applied

Recent Advances in the Synthesis of Difluorinated Architectures from Trifluoromethyl Groups

Feng Zhao et al.

Summary: This review summarizes the recent developments of new methods for the synthesis of difluoromethyl motifs or difluoroalkenes from trifluoromethylated aromatic compounds or trifluoromethyl alkenes via single C(sp(3))-F bond cleavage.

ADVANCED SYNTHESIS & CATALYSIS (2022)

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Review Chemistry, Multidisciplinary

Photoredox-Catalyzed C-H Functionalization Reactions

Natalie Holmberg-Douglas et al.

Summary: The fields of C-H functionalization and photoredox catalysis have gained significant interest and utility in various scientific disciplines. This review focuses on the use of photoredox catalysis in C-H functionalization reactions, highlighting both inorganic/organometallic and organic-based photoredox catalytic systems. The subdivision by reaction class (sp(2) or sp(3) C-H functionalization) provides perspective and tactical strategies for synthetic applications.

CHEMICAL REVIEWS (2022)

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Article Chemistry, Organic

Photocatalytic Synthesis of Diarylmethyl Silanes via 1,6-Conjugate Addition of Silyl Radicals to p-Quinone Methides

Cong Luo et al.

Summary: A novel photocatalytic method for the preparation of diarylmethyl silanes was reported through silyl radicals addition strategy to p-QMs. The method could tolerate a variety of functional groups and provide moderate to excellent yields. The resulting silylation products could be easily converted into a series of bioactive GPR40 agonists and useful p-QMs precursors for the synthesis of compounds possessing both quaternary carbon centers and silicon substituents through simple operation. A plausible mechanism of silyl radicals to p-QMs was proposed based on experimental results and previous literature.

JOURNAL OF ORGANIC CHEMISTRY (2022)

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Review Chemistry, Multidisciplinary

Visible Light-Driven Radical-Mediated C-C Bond Cleavage/Functionalization in Organic Synthesis

Xiao-Ye Yu et al.

Summary: In recent years, visible light photoredox-catalyzed radical-mediated C-C bond cleavage reactions have emerged as a powerful alternative method for overcoming the thermodynamic and kinetic barrier of C-C bond cleavage in diverse molecular scaffolds. These reactions provide an efficient way to construct structurally diverse molecular skeletons, contributing to the development in the field of synthetic organic chemistry.

CHEMICAL REVIEWS (2021)

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Review Chemistry, Multidisciplinary

Recent advances in synthesis of organosilicons via radical strategies

Xueping Zhang et al.

Summary: This article reviews the research progress in the synthesis of organosilicon compounds by free radical pathways since 2016, mainly achieved through the reaction of silyl radicals triggered by peroxide, transition-metal-induced peroxide decomposition, alkali, and photocatalysis.

CHINESE CHEMICAL LETTERS (2021)

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Article Chemistry, Multidisciplinary

Chemoselective Cleavage of Si-C(sp3) Bonds in Unactivated Tetraalkylsilanes Using Iodine Tris(trifluoroacetate)

Keitaro Matsuoka et al.

Summary: In this study, a novel method for chemoselective cleavage of unactivated tetraalkylsilanes under mild conditions using iodine tris(trifluoroacetate) was reported. The reaction enables subsequent synthetic reactions and provides highly stable synthetic precursors for organic synthesis.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Review Chemistry, Multidisciplinary

Quinuclidine and its derivatives as hydrogen-atom-transfer catalysts in photoinduced reactions

Wei Xiao et al.

Summary: Quinuclidine and its derivatives as HAT catalysts show unique characteristics in direct C == H functionalization of compounds with various groups by abstracting electron-rich and hydridic hydrogens. Their application potential in this field is highlighted due to these features.

CHINESE CHEMICAL LETTERS (2021)

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Article Chemistry, Organic

Photoredox-Catalyzed Difunctionalization of Unactivated Olefins for Synthesizing Lactam-Substituted gem-Difluoroalkenes

Jie Shi et al.

Summary: A photoredox-catalyzed radical cascade reaction has been developed for the synthesis of lactam-substituted gem-difluoroalkenes, providing a simple method with good functional group tolerance and high yields.

ORGANIC LETTERS (2021)

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Article Electrochemistry

Reduced Gassing In Lithium-Ion Batteries With Organosilicon Additives

Sarah L. Guillot et al.

Summary: Research has been conducted on the application of organosilicon additives in new lithium-ion battery electrolytes, demonstrating their significant reduction in gas emissions while maintaining battery performance.

JOURNAL OF THE ELECTROCHEMICAL SOCIETY (2021)

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Article Chemistry, Organic

Photoredox/Hydrogen Atom Transfer Cocatalyzed C-H Difluoroallylation of Amides, Ethers, and Alkyl Aldehydes

Yuan-Qiang Guo et al.

Summary: This study introduces a method that combines hydrogen atom transfer and photoredox catalysis to achieve the dehydrogenative difluoroallylation of amides, ethers, and alkyl aldehydes. The method transforms a wide range of substrates into gem-difluoroalkenes via the construction of C(sp(3))-C(sp(3)) or C(sp(3))-C(sp(2)) bonds, with excellent functional group compatibility and high selectivity. It is suitable for late-stage modification of pharmaceutical intermediates due to its versatility in substrate types.

ORGANIC LETTERS (2021)

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Article Chemistry, Organic

Synthesis of β-Silyl α-Amino Acids via Visible-Light-Mediated Hydrosilylation

Yi Wan et al.

Summary: A convenient synthesis of beta-silyl alpha-amino acids was achieved through visible-light-mediated hydrosilylation, using accessible hydrosilanes as substrates with high stereoselectivity. The reaction can also be performed in continuous flow mode and scaled up for gram-scale production.

ORGANIC LETTERS (2021)

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Article Chemistry, Applied

Synthesis of Dibenzosiloles through Electrocatalytic Sila-Friedel-Crafts Reaction

Pan Han et al.

Summary: A novel electrocatalyzed method has been developed for the preparation of dibenzosiloles from biarylhydrosilanes using an intramolecular C-H/Si-H dehydrogenative coupling strategy. Both electro-donating and electro-withdrawing substitution groups were tolerated for this transformation, and the desired dibenzosilole products could be obtained in moderate to excellent yields. A sila-Friedel-Crafts reaction mechanism was proposed based on previous literature and controlled experiments.

ADVANCED SYNTHESIS & CATALYSIS (2021)

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Article Chemistry, Multidisciplinary

Site-Selective Defluorinative sp3 C-H Alkylation of Secondary Amides

Wen-Jun Yue et al.

Summary: This new method features mild conditions, wide applicability, and exquisite site-selectivity, allowing for the rapid and reliable incorporation of gemdifluoroalkene motifs into previously unfunctionalized sp(3) sites, thus providing a new platform for introducing carbonyl isosteres at saturated hydrocarbon sites.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Organic

Visible-Light-Mediated Divergent Silylfunctionalization of Alkenes

Ming Zheng et al.

Summary: This study presents a visible-light-mediated divergent 1,2-silylfunctionalization of alkenes under ambient conditions, yielding a variety of silanes including beta-alkoxy, beta-alkylthio, beta-hydroxy, and beta-indolyl silanes. Vinylsilanes were also successfully prepared without the need for an additional nucleophile.

ORGANIC LETTERS (2021)

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Article Chemistry, Organic

Visible-Light-Mediated C-I Difluoroallylation with an α-Aminoalkyl Radical as a Mediator

Fuyang Yue et al.

Summary: This protocol involves direct visible-light-mediated C-I difluoroallylation reactions of α-trifluoromethyl arylalkenes with alkyl iodides at room temperature using an alpha-aminoalkyl radical as a mediator. It allows efficient functionalization of various alpha-trifluoromethyl arylalkenes with cyclic and acyclic primary, secondary, and tertiary alkyl iodides and is scalable to gram level. The mild protocol using an inexpensive mediator is suitable for late-stage functionalization of complex natural products and drugs.

ORGANIC LETTERS (2021)

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Review Chemistry, Organic

Progress in Visible-Light Catalyzed C-F Bond Functionalization of gem-Difluoroalkenes

Zhiqing Li et al.

Summary: Monofluoroalkene structural units are widely present in complex functional molecules such as drugs and natural products. Developing green, economical and efficient methods for synthesizing monofluoroalkenes is of great scientific significance and practical value. Functionalization of the C-F bond of gem-difluoroalkenes is an effective method to prepare monofluoroalkenes, and research progress in this area using visible-light redox catalysis and visible-light redox/transition-metal synergistic catalysis is summarized.

CHINESE JOURNAL OF ORGANIC CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Advances in silylation and borylation of fluoroarenes and gem-difluoroalkenes via C-F bond cleavage

Juan Zhang et al.

Summary: Organoboron and organosilane compounds are widely used in organic synthesis and pharmaceuticals. The functionalization of the C-F bond provides opportunities for the development of new medicinal compounds. Late-stage functionalization through defluoroborylation and defluorosilylation reactions shows promise in diversifying structures and creating new ideas for further research in this field.

CHEMICAL COMMUNICATIONS (2021)

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Article Chemistry, Multidisciplinary

Photoredox relay-catalyzed gem-difluoroallylation of alkyl iodides

Yuanqiang Guo et al.

Summary: A new example of relay catalysis using a combination of Mn-2(CO)(10) and an iridium-based photocatalyst has been reported. The Mn catalyst and iridium-based photocatalyst catalyze the reaction at different stages in the desired sequence under the same reaction conditions, transforming alkyl iodides into gem-difluoroalkenes with good functional group tolerance. This convenient method is suitable for late-stage modification of multifunctional complex molecules.

CHEMICAL COMMUNICATIONS (2021)

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Review Chemistry, Organic

Visible-light-induced silylation: an update

Sumit Ghosh et al.

Summary: Over the past two decades, visible-light-driven functionalization of various organic systems has achieved great success, reaching impressive levels of complexity and efficiency. Organosilicon compounds are significant due to their promising applications in various fields and they are known for being cheap, easily handled, highly stable, and less toxic. Therefore, there is now a high demand for environmentally friendly synthetic approaches, such as visible-light-induced silylation, for molecule construction with C-Si bonds.

ORGANIC & BIOMOLECULAR CHEMISTRY (2021)

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Review Chemistry, Organic

Recent advance in the C-F bond functionalization of trifluoromethyl-containing compounds

Guobing Yan et al.

Summary: Activation of C-F bonds in trifluoromethyl-containing compounds is a challenging task in organic synthesis, with significant progress being made in the past decades mainly involving trifluoromethylalkenes, trifluoromethylated aromatic and alkyl compounds, among others.

ORGANIC CHEMISTRY FRONTIERS (2021)

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Article Chemistry, Multidisciplinary

Organic photoredox catalyzed C-H silylation of quinoxalinones or electron-deficient heteroarenes under ambient air conditions

Changhui Dai et al.

Summary: Direct C-H silylation of quinoxalinones was achieved using organic photoredox catalysis and hydrogen atom transfer, under transition metal- and external oxidant-free conditions. A range of silylated quinoxalinones with diverse functional groups were synthesized in moderate to high yields, and the methodology was also applicable to electron-deficient heteroarenes.

GREEN CHEMISTRY (2021)

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Article Chemistry, Multidisciplinary

Ring Expansion to 6-, 7-, and 8-Membered Benzosilacycles through Strain-Release Silicon-based Cross-Coupling

Ying Qin et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2020)

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Article Chemistry, Organic

Visible-Light-Mediated β-C-H gem-Difluoroallylation of Aldehydes and Cyclic eKetones through C-F Bond Cleavage of 1-Trifluoromethyl Alkenes

Devireddy Anand et al.

ORGANIC LETTERS (2020)

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Article Chemistry, Organic

Visible-Light-Induced Deoxygenation/Defluorination Protocol for Synthesis of γ,γ-Difluoroallylic Ketones

Yuan-Qiang Guo et al.

ORGANIC LETTERS (2020)

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Review Chemistry, Multidisciplinary

Methodologies and Strategies for Selective Borylation of C-Het and C-C Bonds

Minyan Wang et al.

CHEMICAL REVIEWS (2020)

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Article Chemistry, Physical

Hydrogen storage in organosilicon ionic liquids

Grigory S. Deyko et al.

INTERNATIONAL JOURNAL OF HYDROGEN ENERGY (2020)

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Article Chemistry, Organic

Enantioselective copper-catalysed defluorosilylation of trifluoro-methylated alkenes with silylboronates

Pan Gao et al.

ORGANIC CHEMISTRY FRONTIERS (2020)

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Review Chemistry, Multidisciplinary

Recent advances in three-component difunctionalization ofgem-difluoroalkenes

Chi Liu et al.

CHEMICAL COMMUNICATIONS (2020)

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Review Chemistry, Multidisciplinary

Catalytic C(sp3)-F bond formation: recent achievements and pertaining challenges

Giulia Tarantino et al.

GREEN CHEMISTRY (2020)

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Review Chemistry, Multidisciplinary

Transition-Metal-Mediated and -Catalyzed C-F Bond Activation by Fluorine Elimination

Takeshi Fujita et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Article Chemistry, Organic

Visible-Light-Promoted Redox Neutral γ,γ-Difluoroallylation of Cycloketone Oxime Ethers with Trifluoromethyl Alkenes via C-C and C-F Bond Cleavage

Yuwei He et al.

ORGANIC LETTERS (2019)

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Article Chemistry, Multidisciplinary

Dehydrogenative Silylation of Alkenes for the Synthesis of Substituted Allylsilanes by Photoredox, Hydrogen-Atom Transfer, and Cobalt Catalysis

Wan-Lei Yu et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Article Chemistry, Multidisciplinary

Transition-Metal-Free Defluorosilylation of Fluoroalkenes with Silylboronates

Pan Gao et al.

CHINESE JOURNAL OF CHEMISTRY (2019)

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Article Chemistry, Multidisciplinary

Defluorosilylation of Industrially Relevant Fluoroolefins Using Nucleophilic Silicon Reagents

Greg Coates et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2019)

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Article Chemistry, Multidisciplinary

Catalytic Enantioselective Boryl and Silyl Substitution with Trifluoromethyl Alkenes: Scope, Utility, and Mechanistic Nuances of Cu-F β-Elimination

Paulo H. S. Paioti et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2019)

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Article Chemistry, Multidisciplinary

Metal-free defluorinative arylation of trifluoromethyl alkenes via photoredox catalysis

Rebecca J. Wiles et al.

CHEMICAL COMMUNICATIONS (2019)

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Review Chemistry, Physical

Polymeric and ceramic silicon-based coatings - a review

Gilvan Barroso et al.

JOURNAL OF MATERIALS CHEMISTRY A (2019)

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Article Chemistry, Multidisciplinary

Visible-light-mediated deuteration of silanes with deuterium oxide

Rong Zhou et al.

CHEMICAL SCIENCE (2019)

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Review Chemistry, Multidisciplinary

Recent advances in the synthesis and applications of α-(trifluoromethyl)styrenes in organic synthesis

Feitao Tian et al.

CHEMICAL COMMUNICATIONS (2019)

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Article Chemistry, Medicinal

Quest for Novel Chemical Entities through Incorporation of Silicon in Drug Scaffolds

Remya Ramesh et al.

JOURNAL OF MEDICINAL CHEMISTRY (2018)

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Article Chemistry, Medicinal

Fluorine and Fluorinated Motifs in the Design and Application of Bioisosteres for Drug Design

Nicholas A. Meanwell

JOURNAL OF MEDICINAL CHEMISTRY (2018)

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Article Chemistry, Multidisciplinary

Visible-Light-Mediated Metal-Free Difunctionalization of Alkenes with CO2 and Silanes or C(sp3)-H Alkanes

Jing Hou et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Article Chemistry, Multidisciplinary

Fluorinated Vinylsilanes from the Copper-Catalyzed Defluorosilylation of Fluoroalkene Feedstocks

Hironobu Sakaguchi et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2018)

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Review Chemistry, Physical

Recent Developments in the Photo-Mediated Generation of Silyl Radicals and Their Application in Organic Synthesis

Jie-Sheng Li et al.

CHEMPHOTOCHEM (2018)

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Review Chemistry, Physical

Recent Advances in Transition-Metal-Catalyzed Synthetic Transformations of Organosilicon Reagents

Takeshi Komiyama et al.

ACS CATALYSIS (2017)

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Review Chemistry, Medicinal

Progress in the medicinal chemistry of silicon: C/Si exchange and beyond

Shinya Fujii et al.

FUTURE MEDICINAL CHEMISTRY (2017)

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Article Chemistry, Physical

Photoredox-Mediated Routes to Radicals: The Value of Catalytic Radical Generation in Synthetic Methods Development

Jennifer K. Matsui et al.

ACS CATALYSIS (2017)

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Article Chemistry, Multidisciplinary

Visible-Light-Mediated Metal-Free Hydrosilylation of Alkenes through Selective Hydrogen Atom Transfer for Si-H Activation

Rong Zhou et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

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Article Chemistry, Multidisciplinary

Photoredox Generation of Carbon-Centered Radicals Enables the Construction of 1,1-Difluoroalkene Carbonyl Mimics

Simon B. Lang et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2017)

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Article Chemistry, Multidisciplinary

Visible-Light-Mediated Two-Fold Unsymmetrical C(sp3)-H Functionalization and Double C-F Substitution

Linyong Li et al.

CHEMISTRY-A EUROPEAN JOURNAL (2017)

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Review Chemistry, Multidisciplinary

Carbon-Carbon Bond Forming Reactions via Photogenerated Intermediates

Davide Ravelli et al.

CHEMICAL REVIEWS (2016)

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Review Chemistry, Multidisciplinary

Organic Photoredox Catalysis

Nathan A. Romero et al.

CHEMICAL REVIEWS (2016)

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Article Chemistry, Organic

Synthesis of Functionalized gem-Difluoroalkenes via a Photocatalytic Decarboxylative/Defluorinative Reaction

Tiebo Xiao et al.

JOURNAL OF ORGANIC CHEMISTRY (2016)

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Article Chemistry, Physical

Donor-Acceptor Fluorophores for Visible-Light-Promoted Organic Synthesis:Photoredox/Ni Dual Catalytic C(sp3)-C(sp2) Cross-Coupling

Jian Luo et al.

ACS CATALYSIS (2016)

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Review Chemistry, Multidisciplinary

Carbon Trifluoromethylation Reactions of Hydrocarbon Derivatives and Heteroarenes

Concepcion Alonso et al.

CHEMICAL REVIEWS (2015)

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Article Multidisciplinary Sciences

O-H hydrogen bonding promotes H-atom transfer from α C-H bonds for C-alkylation of alcohols

Jenna L. Jeffrey et al.

SCIENCE (2015)

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Review Chemistry, Multidisciplinary

Fluorinated Proteins: From Design and Synthesis to Structure and Stability

E. Neil G. Marsh

ACCOUNTS OF CHEMICAL RESEARCH (2014)

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Review Chemistry, Multidisciplinary

Fluorine in Pharmaceutical Industry: Fluorine-Containing Drugs Introduced to the Market in the Last Decade (2001-2011)

Jiang Wang et al.

CHEMICAL REVIEWS (2014)

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Review Chemistry, Multidisciplinary

Activation of the Si-B Interelement Bond: Mechanism, Catalysis, and Synthesis

Martin Oestreich et al.

CHEMICAL REVIEWS (2013)

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Article Chemistry, Medicinal

Organosilicon Molecules with Medicinal Applications

Annaliese K. Franz et al.

JOURNAL OF MEDICINAL CHEMISTRY (2013)

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Review Chemistry, Multidisciplinary

Visible-Light Photoredox Catalysis

Jun Xuan et al.

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION (2012)

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Review Chemistry, Multidisciplinary

Asymmetric Construction of Stereogenic Carbon Centers Featuring a Trifluoromethyl Group from Prochiral Trifluoromethylated Substrates

Jing Nie et al.

CHEMICAL REVIEWS (2011)

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Review Chemistry, Multidisciplinary

Silicon-based cross-coupling reaction: an environmentally benign version

Yoshiaki Nakao et al.

CHEMICAL SOCIETY REVIEWS (2011)

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Article Chemistry, Medicinal

Synopsis of Some Recent Tactical Application of Bioisosteres in Drug Design

Nicholas A. Meanwell

JOURNAL OF MEDICINAL CHEMISTRY (2011)

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Article Chemistry, Multidisciplinary

Visible light photocatalysis as a greener approach to photochemical synthesis

Tehshik P. Yoon et al.

NATURE CHEMISTRY (2010)

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Article Chemistry, Multidisciplinary

Silylboranes as New Tools in Organic Synthesis

Toshimichi Ohmura et al.

BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN (2009)

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Review Chemistry, Medicinal

Silicon switches of marketed drugs

P. K. Pooni et al.

MINI-REVIEWS IN MEDICINAL CHEMISTRY (2006)

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Article Chemistry, Inorganic & Nuclear

Fluoro-artemisinins:: When a gem-difluoroethylene replaces a carbonyl group

Guillaume Magueur et al.

JOURNAL OF FLUORINE CHEMISTRY (2006)

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Review Pharmacology & Pharmacy

Exploitation of silicon medicinal chemistry in drug discovery

JS Mills et al.

EXPERT OPINION ON INVESTIGATIONAL DRUGS (2004)

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Article Chemistry, Medicinal

Design, synthesis, and biological activity of a difluoro-substituted, conformationally rigid vigabatrin analogue as a potent γ-aminobutyric acid aminotransferase inhibitor

Y Pan et al.

JOURNAL OF MEDICINAL CHEMISTRY (2003)

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Article Chemistry, Multidisciplinary

Reversal of the apparent regiospecificity of NAD(P)H-dependent hydride transfer: The properties of the difluoromethylene group, a carbonyl mimic

C Leriche et al.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2003)

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Article Chemistry, Organic

Synthesis of novel D-2′-deoxy-2′-C-difluoromethylene-4′-thiocytidine as a potential antitumor agent

MH Lim et al.

ORGANIC LETTERS (2002)

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Photoredox Metal-Free Allylic Defluorinative Silylation of α-Trifluoromethylstyrenes with Hydrosilanes

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