Recent Advances of CO<sub>2</sub> Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules

Guo, Xiao; Wang, Yazhou; Chen, Jie; Li, Gongqiang; Xia, Ji‐Bao

doi:10.6023/cjoc202002032

Cited by 34 publications

(9 citation statements)

References 79 publications

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“…Also, the direct carboxylation of general sp 3 C–H bonds, beyond the allylic and benzylic positions, ought to be addressed . Third, there is still a lack of reports on enantioselective carboxylative cyclization and carboxylation, which would be a practical way to provide pharmaceutical and bioactive scaffolds . Finally, the single-electron activation of CO 2 and its application in carboxylation reactions remains in its infancy.…”

Section: Discussionmentioning

confidence: 99%

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Huang

et al. 2021

Acc. Chem. Res.

230

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Metrics & MoreArticle Recommendations CONSPECTUS: Carbon dioxide (CO 2 ) is not only a greenhouse gas and a common waste product but also an inexpensive, readily available, and renewable carbon resource. It is an important one-carbon (C1) building block in organic synthesis for the construction of valuable compounds. However, its utilization is challenging owing to its thermodynamic stability and kinetic inertness. Although significant progress has been achieved, many limitations remain in this field with regard to the substrate scope, reaction system, and activation strategies. Since 2015, our group has focused on CO 2 utilization in organic synthesis. We are also interested in the vast possibilities of radical chemistry, although the high reactivity of radicals presents challenges in controlling selectivity. We hope to develop highly useful CO 2 transformations involving radicals by achieving a balance of reactivity and selectivity under mild reaction conditions. Over the past 6 years, we along with other experts have disclosed radical-type carboxylative cyclizations and carboxylations using CO 2 .We initiated our research by realizing the Cu-catalyzed radical-type oxytrifluoromethylation of allylamines and heteroaryl methylamines to generate valuable 2-oxazolidones with various radical precursors. Apart from Cu catalysis, visible-light photoredox catalysis is also a powerful method to achieve efficient carboxylative cyclization. In these cases, single-electron-oxidation-promoted C−O bond formation between benzylic radicals and carbamates is the key step. Since carboxylic acids exist widely in natural products and bioactive drugs and serve as important bulk chemicals in industry, we realized further visible-light-promoted carboxylations with CO 2 to construct such chemicals. We have achieved the selective umpolung carboxylations of imines, enamides, tetraalkylammonium salts, and oxime esters by successive single-electron-transfer (SSET) reduction. Using this strategy, we have also realized the dearomative arylcarboxylation of indoles with CO 2 . In addition to the incorporation of 1 equiv of CO 2 per substrate, we have recently developed a visible-light photoredox-catalyzed dicarboxylation of alkenes, allenes, and (hetero)arenes via SSET reduction, which allows the incorporation of two CO 2 molecules into organic compounds to generate valuable diacids as polymer precursors.In addition to the two-electron activation of CO 2 , we sought to develop new strategies to realize efficient and selective transformations via single-electron activation of CO 2 . Inspired by the hypothetical electron-transfer mechanism of iron−sulfur proteins, we have realized the visible-light-driven thiocarboxylation of alkenes with CO 2 using catalytic iron salts as promoters. The in-situ-generated Fe/S complexes are likely able to reduce CO 2 to its radical anion, which could react with alkenes to give a stabilized carbon radical. Moreover, we have also disclosed charge-transfer complex (CTC) formation between thiolate and acrylate/styr...

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Section: Discussionmentioning

confidence: 99%

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Huang

et al. 2021

Acc. Chem. Res.

230

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“…Carbon dioxide (CO 2 ) is an abundant, nontoxic, and renewable C1 feedstock. Its synthetic transformation has received great attentions. , Reductive coupling of readily available free alcohols and CO 2 would provide a straightforward route to carboxylic acids. Coupling of alcohol or its derived esters (preactivated alcohols) with CO 2 to carboxylic acids has been reported via Ni-, Co-, or Pd-catalyzed reductive coupling reactions in the presence of an excess amount of metal reductant or under electrochemical conditions .…”

Section: Introductionmentioning

confidence: 99%

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO₂ via Photoredox Catalysis

et al. 2022

J. Am. Chem. Soc.

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A new strategy for the direct cleavage of the C(sp3)–OH bond has been developed via activation of free alcohols with neutral diphenyl boryl radical generated from sodium tetraphenylborate under mild visible light photoredox conditions. This strategy has been verified by cross-electrophile coupling of free alcohols and carbon dioxide for the synthesis of carboxylic acids. Direct transformation of a range of primary, secondary, and tertiary benzyl alcohols to acids has been achieved. Control experiments and computational studies indicate that activation of alcohols with neutral boryl radical undergoes homolysis of the C(sp3)–OH bond, generating alkyl radicals. After reducing the alkyl radical into carbon anion under photoredox conditions, the following carboxylation with CO2 affords the coupling product.

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“…However, these reports could provide only achiral or racemic dicarboxylic acids. Although asymmetric transformations with CO 2 are of great interest, − asymmetric dicarboxylation with CO 2 to form chiral dicarboxylic acids, especially the catalytic asymmetric variant, has not been disclosed yet.…”

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confidence: 99%

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

Gui,

Chen,

et al. 2024

J. Am. Chem. Soc.

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Dicarboxylic acids and derivatives are important building blocks in organic synthesis, biochemistry, and the polymer industry. Although catalytic dicarboxylation with CO 2 represents a straightforward and sustainable route to dicarboxylic acids, it is still highly challenging and limited to generation of achiral or racemic dicarboxylic acids. To date, catalytic asymmetric dicarboxylation with CO 2 to give chiral dicarboxylic acids has not been reported. Herein, we report the first asymmetric dicarboxylation of 1,3-dienes with CO 2 via Cu catalysis. This strategy provides an efficient and environmentally benign route to chiral dicarboxylic acids with high regio-, chemo-, and enantioselectivities. The copper self-relay catalysis, that is, Cu-catalyzed boracarboxylation of 1,3-dienes to give carboxylated allyl boronic ester intermediates and subsequent carboxylation of C−B bonds to give dicarboxylates, is key to the success of this dicarboxylation. Moreover, this protocol exhibits broad substrate scope, good functional group tolerance, easy product derivatizations, and facile synthesis of chiral liquid crystalline polyester and drug-like scaffolds.

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Recent Advances of CO₂ Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules

Cited by 34 publications

References 79 publications

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO₂ via Photoredox Catalysis

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂

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Recent Advances of CO2 Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules

Cited by 34 publications

References 79 publications

Radical Carboxylative Cyclizations and Carboxylations with CO2

Radical Carboxylative Cyclizations and Carboxylations with CO2

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO2 via Photoredox Catalysis

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO2

Contact Info

Product

Resources

About

Recent Advances of CO₂ Fixation via Asymmetric Catalysis for the Direct Synthesis of Optically Active Small Molecules

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Boryl Radical Activation of Benzylic C–OH Bond: Cross-Electrophile Coupling of Free Alcohols and CO₂ via Photoredox Catalysis

Cu-Catalyzed Asymmetric Dicarboxylation of 1,3-Dienes with CO₂