Cu(II)-Catalyzed Phosphonocarboxylative Cyclization Reaction of Propargylic Amines and Phosphine Oxide with CO<sub>2</sub>

Huang, Weixing; Ren, Fang‐Yu; Wang, Mingwei; Qiu, Li−Qi; Chen, Kaihong; He, Liang‐Nian

doi:10.1021/acs.joc.0c02172

Cited by 32 publications

(15 citation statements)

References 71 publications

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“…The following process is similar to our previous reports. Apart from carbon radicals, recently He’s group has also reported a novel Cu(II)-catalyzed phosphonocarboxylative cyclization reaction of propargylic amines and phosphine oxides with CO 2 …”

Section: Synthetic Methods Developmentmentioning

confidence: 99%

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Huang

et al. 2021

Acc. Chem. Res.

296

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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: Synthetic Methods Developmentmentioning

confidence: 99%

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Huang

et al. 2021

Acc. Chem. Res.

296

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“…Scheme 36. He's Cu-catalyzed carbamation of various phosphonate-functionalized propargylic amines [69].…”

Section: Homogeneous Catalystsmentioning

confidence: 99%

Recent Advances in the Synthesis of Five-Membered Cyclic Carbonates and Carbamates from Allylic or Propargylic Substrates and CO2

et al. 2022

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The organic carbamates and carbonates are highly desirable compounds that have found a wide range of applications in drug design, medicinal chemistry, material science, and the polymer industry. The development of new catalytic carbonate and carbamate forming reactions, which employ carbon dioxide as a cheap, green, abundant, and easily available reagent, would thus represent an ideal substitution for existing methods. In this review, the advancements in the catalytic conversion of allylic and propargylic alcohols and amines to corresponding five-membered cyclic carbonates and carbamates are summarized. Both the metal- and the organocatalyzed methods are reviewed, as well as the proposed mechanisms and key intermediates of the illustrated carbonate and carbamate forming reactions.

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“…In 2020, Hou et al [89] described intermolecular hydrophosphorylative cyclizations of enynes and dienes to access heterocycles under visible-light irradiation [Figure 56]. The phosphinoyl radicals were formed via direct HAT between the phosphine oxides and photoexcited catalyst.…”

Section: Radical Cascade Cyclization Phosphorylation Of Alkynesmentioning

confidence: 99%

Advances in radical phosphorylation from 2016 to 2021

Liu¹,

Xiao²,

Fu³

et al. 2021

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Organophosphorus compounds are of great significance in organic chemistry. Therefore, the construction of phosphorus-containing compounds has attracted significant attention from organic chemists. Radical phosphorylation has become a powerful strategy for building organophosphorus compounds and numerous achievements have been realized in recent years. In this review, we summarize the development of the generation and application of phosphorus radicals in organic chemistry since 2016. Special emphasis is given to various new transformations involving the generation of P-centered radicals via transition metal catalytic, photochemical and electrochemical means. Recent advances in the development of metal-free catalytic phosphorylations involving Pcentered radicals are also reviewed.

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Cu(II)-Catalyzed Phosphonocarboxylative Cyclization Reaction of Propargylic Amines and Phosphine Oxide with CO₂

Cited by 32 publications

References 71 publications

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Recent Advances in the Synthesis of Five-Membered Cyclic Carbonates and Carbamates from Allylic or Propargylic Substrates and CO2

Advances in radical phosphorylation from 2016 to 2021

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Cu(II)-Catalyzed Phosphonocarboxylative Cyclization Reaction of Propargylic Amines and Phosphine Oxide with CO2

Cited by 32 publications

References 71 publications

Radical Carboxylative Cyclizations and Carboxylations with CO2

Radical Carboxylative Cyclizations and Carboxylations with CO2

Recent Advances in the Synthesis of Five-Membered Cyclic Carbonates and Carbamates from Allylic or Propargylic Substrates and CO2

Advances in radical phosphorylation from 2016 to 2021

Contact Info

Product

Resources

About

Cu(II)-Catalyzed Phosphonocarboxylative Cyclization Reaction of Propargylic Amines and Phosphine Oxide with CO₂

Radical Carboxylative Cyclizations and Carboxylations with CO₂

Radical Carboxylative Cyclizations and Carboxylations with CO₂