Visible-Light-Promoted Asymmetric Catalysis by Chiral Complexes of First-Row Transition Metals

This short review presents an overview of visible-light-driven asymmetric catalysis by chiral complexes of first-row transition metals. The processes described here include dual catalysis by a chiral complex of copper, nickel, cobalt or chromium and an additional photoredox or energy-transfer catalyst, and bifunctional catalysis by a single chiral copper or nickel catalyst. These methods allow valuable transformations with high functional group compatibility. They provide stereoselective construction of carbon-carbon or carbon-heteroatom bonds under mild conditions, and produce a diverse range of previously unknown enantio-enriched compounds.

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Advancements in Visible-Light-Enabled Radical C(sp)2–H Alkylation of (Hetero)arenes

Synthesis ◽

10.1055/s-0037-1611658 ◽

2019 ◽

Vol 51 (05) ◽

pp. 1063-1072 ◽

Cited By ~ 21

Author(s):

Alexandra Sun ◽

Rory McAtee ◽

Edward McClain ◽

Corey Stephenson

Keyword(s):

Carboxylic Acid ◽

Visible Light ◽

Alkyl Radical ◽

Functional Group ◽

Short Review ◽

Alkyl Halides ◽

Research Development ◽

Visible Light Driven ◽

Radical Generation ◽

Operational Simplicity

The Minisci reaction, which encompasses the radical C–H alkylation of heteroarenes, has undergone revolutionary development in recent years. The application of photoredox catalysis to alkyl radical generation has given rise to a multitude of methods that feature enhanced functional group tolerance, generality, and operational simplicity. The intent of this short review is to bring readers up to date on this rapidly expanding field. Specifically, we will highlight key examples of visible-light-driven Minisci alkylation strategies that represent key advancements in this area of research. The scope and limitations of these transformations will be discussed, with a focus on examining the underlying pathways for alkyl radical generation. Our goal is to make this short review a stepping stone for further synthetic research development. Sections are organized based on alkyl radical precursor reagents.1 Introduction2 Alkyl Carboxylic Acids and Carboxylic Acid Derivatives3 Alkylboronic Acids4 Potassium Alkyl- and Alkoxymethyltrifluoroborates5 Alkyl Halides6 Alcohols and Ethers7 Conclusion

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Dehydrogenative 6π Heterocyclization under Visible Light Irradiation and Mechanistic Insights

Organic Chemistry Frontiers ◽

10.1039/d1qo00356a ◽

2021 ◽

Author(s):

Zhao Zhang ◽

Haohua Chen ◽

Niklas Keller ◽

Qin Xiong ◽

Lei Liu ◽

...

Keyword(s):

Transition Metals ◽

Visible Light ◽

Visible Light Irradiation ◽

Light Irradiation ◽

Reaction Proceeds ◽

Visible Light Driven

A visible-light-driven oxidative 6π heterocycilization for the synthesis of structurally diverse π-conjugated polycyclic 1-aminoisoquinolines has been developed. The reaction proceeds under visible-light or sunshine, obviates photocatalyst and transition-metals, and features...

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Bromotrifluoromethane: A Useful Reagent for Hydrotrifluoromethylation of Alkenes and Alkynes

Synlett ◽

10.1055/s-0036-1591944 ◽

2018 ◽

Vol 29 (08) ◽

pp. 1028-1032 ◽

Cited By ~ 5

Author(s):

Xing Zheng ◽

Xingang Zhang ◽

Yu-Yan Ren

Keyword(s):

Visible Light ◽

Organic Synthesis ◽

Functional Group ◽

Mild Conditions ◽

Industrial Material ◽

Reaction Proceeds

Bromotrifluoromethane (CF3Br) is a simple, inexpensive and abundant industrial material employed as a trifluoromethylating reagent. However, only limited strategies using CF3Br as a fluorine source are reported. Herein, we describe a visible-light-induced hydrotrifluoromethylation of alkenes and alkynes with CF3Br. The reaction proceeds under mild conditions with good functional group tolerance, providing a new route for the application of BrCF3 in organic synthesis.

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Photocatalytic Synthesis of Tetra-Substituted Furans Promoted by Carbon Dioxide

Chemical Science ◽

10.1039/d1sc06403g ◽

2021 ◽

Author(s):

Ya-Ming Tian ◽

Huaiju Wang ◽

Ritu Ritu ◽

Burkhard Koenig

Keyword(s):

Carbon Dioxide ◽

Transition Metal ◽

Visible Light ◽

Metal Free ◽

Mild Conditions ◽

Simple Protocol ◽

Visible Light Driven ◽

Substituted Furans ◽

Photocatalytic Synthesis

We report a simple protocol for the transition metal-free, visible-light-driven conversion of 1,3-diketones to tetra-substituted furan skeleton compounds in carbon dioxide (CO2) atmosphere under mild conditions. It was found that...

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Visible-Light-Induced Radical Polynitration of Arylboronic Acids: Synthesis of Polynitrophenols

Synthesis ◽

10.1055/s-0037-1610038 ◽

2018 ◽

Vol 50 (15) ◽

pp. 2891-2896 ◽

Cited By ~ 1

Author(s):

Jinna Song ◽

Xihe Bi ◽

Qi Zhang ◽

Kaki Raveendra Babu ◽

Zhouliang Huang

Keyword(s):

Visible Light ◽

Aromatic Compounds ◽

Functional Group ◽

Simple Procedure ◽

One Pot ◽

Arylboronic Acids ◽

Mild Conditions ◽

Conventional Methods ◽

Straightforward Approach

We report a visible light-assisted one-pot method for the synthesis of polynitrophenols through radical tandem hydroxylation and nitration of arylboronic acids by utilizing copper(II) nitrate trihydrate as the nitro source. This method features mild conditions, a simple procedure, and good functional group tolerance. Compared to conventional methods, this work provides a straightforward approach for the polynitration of aromatic compounds.

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Screening Commercial Semiconductors for Visible Light Driven Asymmetric Catalysis

Particle & Particle Systems Characterization ◽

10.1002/ppsc.201700280 ◽

2017 ◽

Vol 35 (1) ◽

pp. 1700280 ◽

Cited By ~ 7

Author(s):

Yin Zhang ◽

Yanfei Zhu ◽

Wencai Zhou ◽

Xueying Qiu ◽

Zhiyong Tang

Keyword(s):

Visible Light ◽

Asymmetric Catalysis ◽

Visible Light Driven

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A mild, general, and metal-free method for site-specific deuteration induced by visible light using D2O as the source of deuterium atoms

Green Chemistry ◽

10.1039/c9gc04096j ◽

2020 ◽

Vol 22 (3) ◽

pp. 669-672 ◽

Cited By ~ 4

Author(s):

Shuai Shi ◽

Ruining Li ◽

Liangming Rao ◽

Zhankui Sun

Keyword(s):

Visible Light ◽

Functional Group ◽

Site Specific ◽

Metal Free ◽

Mild Conditions ◽

Highly Efficient ◽

Radical Approach

Visible light induced desulfurization–deuteration method was developed using D2O as the source of deuterium atoms. This radical approach features mild conditions, broad substrate scope, highly efficient D-incorporation and excellent functional group compatibility.

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Photocatalytic asymmetric epoxidation of trans-stilbene with manganese–porphyrin/graphene-oxide nanocomposite and molecular oxygen: axial ligand effect

Catalysis Science & Technology ◽

10.1039/d0cy00441c ◽

2020 ◽

Vol 10 (10) ◽

pp. 3290-3302 ◽

Cited By ~ 1

Author(s):

Elahe Ahadi ◽

Hassan Hosseini-Monfared ◽

Alex Spieß ◽

Christoph Janiak

Keyword(s):

Graphene Oxide ◽

Visible Light ◽

Molecular Oxygen ◽

Axial Ligand ◽

Asymmetric Epoxidation ◽

Manganese Porphyrin ◽

Ligand Effect ◽

Mild Conditions ◽

Trans Stilbene ◽

Visible Light Driven

An efficient, visible light-driven manganese–porphyrin photocatalyst was developed for the asymmetric epoxidation of trans-stilbene by molecular oxygen under mild conditions.

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Dual Ni/photoredox-catalyzed asymmetric cross-coupling to access chiral benzylic boronic esters

Nature Communications ◽

10.1038/s41467-021-21947-1 ◽

2021 ◽

Vol 12 (1) ◽

Author(s):

Purui Zheng ◽

Pan Zhou ◽

Dong Wang ◽

Wenhao Xu ◽

Hepan Wang ◽

...

Keyword(s):

Visible Light ◽

Ambient Temperature ◽

Functional Group ◽

Cross Coupling ◽

Strong Base ◽

Mild Conditions ◽

Aryl Iodides ◽

Boronic Esters

AbstractThe flourishing Ni/photoredox-catalyzed asymmetric couplings typically rely on redox-neutral reactions. In this work, we report a reductive cross-coupling of aryl iodides and α-chloroboranes under a dual catalytic regime to further enrich the metallaphotoredox chemistry. This approach proceeds under mild conditions (visible light, ambient temperature, no strong base) to access the versatile benzylic boronic esters with good functional group tolerance and excellent enantioselectivities.

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