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Photoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds

Author

Listed:
  • Liang Ge

    (Nanjing Tech University)

  • Chi Zhang

    (Nanjing Tech University)

  • Chengkai Pan

    (Nanjing Tech University)

  • Ding-Xing Wang

    (Nanjing Tech University)

  • Dong-Ying Liu

    (Nanjing Tech University)

  • Zhi-Qiang Li

    (Nanjing Tech University)

  • Pingkang Shen

    (Nanjing Tech University)

  • Lifang Tian

    (Nanjing Tech University)

  • Chao Feng

    (Nanjing Tech University)

Abstract

Sterically congested C–O and C–N bonds are ubiquitous in natural products, pharmaceuticals, and bioactive compounds. However, the development of a general method for the efficient construction of those sterically demanding covalent bonds still remains a formidable challenge. Herein, a photoredox-driven ring-opening C(sp3)–heteroatom bond formation of arylcyclopropanes is presented, which enables the construction of structurally diversified while sterically congested dialkyl ether, alkyl ester, alcohol, amine, chloride/fluoride, azide and also thiocyanate derivatives. The selective single electron oxidation of aryl motif associated with the thermodynamic driving force from ring strain-release is the key for this transformation. By this synergistic activation mode, C–C bond cleavage of otherwise inert cyclopropane framework is successfully unlocked. Further mechanistic and computational studies disclose a complete stereoinversion upon nucleophilic attack, thus proving a concerted SN2-type ring-opening functionalization manifold, while the regioselectivity is subjected to an orbital control scenario.

Suggested Citation

  • Liang Ge & Chi Zhang & Chengkai Pan & Ding-Xing Wang & Dong-Ying Liu & Zhi-Qiang Li & Pingkang Shen & Lifang Tian & Chao Feng, 2022. "Photoredox-catalyzed C–C bond cleavage of cyclopropanes for the formation of C(sp3)–heteroatom bonds," Nature Communications, Nature, vol. 13(1), pages 1-13, December.
    • Handle: RePEc:nat:natcom:v:13:y:2022:i:1:d:10.1038_s41467-022-33602-4
    DOI: 10.1038/s41467-022-33602-4
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    References listed on IDEAS

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    1. Xiaheng Zhang & Russell T. Smith & Chip Le & Stefan J. McCarver & Brock T. Shireman & Nicholas I. Carruthers & David W. C. MacMillan, 2020. "Copper-mediated synthesis of drug-like bicyclopentanes," Nature, Nature, vol. 580(7802), pages 220-226, April.
    2. Liang Ge & Ding-Xing Wang & Renyi Xing & Di Ma & Patrick J. Walsh & Chao Feng, 2019. "Photoredox-catalyzed oxo-amination of aryl cyclopropanes," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
    3. Alison E. Wendlandt & Prithvi Vangal & Eric N. Jacobsen, 2018. "Quaternary stereocentres via an enantioconvergent catalytic SN1 reaction," Nature, Nature, vol. 556(7702), pages 447-451, April.
    4. Sergey V. Pronin & Christopher A. Reiher & Ryan A. Shenvi, 2013. "Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines," Nature, Nature, vol. 501(7466), pages 195-199, September.
    5. Sergey V. Pronin & Christopher A. Reiher & Ryan A. Shenvi, 2013. "Correction: Corrigendum: Stereoinversion of tertiary alcohols to tertiary-alkyl isonitriles and amines," Nature, Nature, vol. 503(7475), pages 300-300, November.
    6. Caiyou Chen & Jonas C. Peters & Gregory C. Fu, 2021. "Photoinduced copper-catalysed asymmetric amidation via ligand cooperativity," Nature, Nature, vol. 596(7871), pages 250-256, August.
    7. Jinbao Xiang & Ming Shang & Yu Kawamata & Helena Lundberg & Solomon H. Reisberg & Miao Chen & Pavel Mykhailiuk & Gregory Beutner & Michael R. Collins & Alyn Davies & Matthew Bel & Gary M. Gallego & Ji, 2019. "Hindered dialkyl ether synthesis with electrogenerated carbocations," Nature, Nature, vol. 573(7774), pages 398-402, September.
    8. Rahul A. Watile & Anon Bunrit & Jèssica Margalef & Sunisa Akkarasamiyo & Rabia Ayub & Emi Lagerspets & Srijit Biswas & Timo Repo & Joseph S. M. Samec, 2019. "Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst," Nature Communications, Nature, vol. 10(1), pages 1-9, December.
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    1. Mingrui Li & Yingtao Wu & Xiao Song & Jiaqiong Sun & Zuxiao Zhang & Guangfan Zheng & Qian Zhang, 2024. "Visible light-mediated organocatalyzed 1,3-aminoacylation of cyclopropane employing N-benzoyl saccharin as bifunctional reagent," Nature Communications, Nature, vol. 15(1), pages 1-9, December.

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