Cleaving arene rings for acyclic alkenylnitrile synthesis - Nature.com

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Abstract

Synthetic chemistry is built around the formation of carbon−carbon bonds. Conversely, selective methods for C−C bond cleavage is a largely unmet challenge^1–6, the solution of which will provide promising applications in synthesis, coal liquefaction, petroleum cracking, polymer degradation and biomass conversion. For example, aromatic rings are ubiquitous skeletal features in inert chemical feed stocks, but are inert to many reaction conditions owing to their aromaticity and low polarity. Over the past century, only a few methods under harsh conditions have achieved direct arene ring modifications involving the cleavage of inert aromatic C−C bonds^7,8, and arene ring-cleavage reactions using stoichiometric transition metal complexes or enzymes in bacteria are still limited^9–11. We now report a copper-catalysed selective arene ring-opening reaction strategy. Our aerobic oxidative copper catalysis converts anilines, arylboronic acids, aryl azides, aryl halides, aryl triflates, aryl trimethylsiloxanes, aryl hydroxamic acids and aryl diazonium salts into alkenyl nitriles through selective C−C bond cleavage of arene rings. This chemistry was applied to the modification of polycyclic aromatics and the preparation of industrially important hexamethylenediamine and adipic acid derivatives. Several examples of late-stage modification of complex molecules and fused ring compounds further support the potential broad utility of this methodology.

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Author information

Author notes

1. These authors contributed equally: Xu Qiu, Yueqian Sang, Hao Wu

Affiliations

1. State Key Laboratory of Natural and Biomimetic Drugs, School of Pharmaceutical Sciences, Peking University, Beijing, China

   Xu Qiu, Hao Wu, Zixi Yan, Yachong Wang, Zengrui Cheng, Xiaoyang Wang, Hui Tan, Song Song, Xiaohui Zhang & Ning Jiao

2. Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, CA, USA

   Xiao-Song Xue & K. N. Houk

3. State Key Laboratory of Elemento-organic Chemistry, College of Chemistry, Nankai University, Tianjin, China

   Yueqian Sang & Xiao-Song Xue

4. Key Laboratory of Green Chemical Media and Reactions, Ministry of Education, School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang, China

   Hao Wu & Guisheng Zhang

5. State Key Laboratory of Organometallic Chemistry, Chinese Academy of Sciences, Shanghai, China

   Ning Jiao

Authors

1. Xu Qiu
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2. Yueqian Sang
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3. Hao Wu
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4. Xiao-Song Xue
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5. Zixi Yan
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6. Yachong Wang
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7. Zengrui Cheng
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8. Xiaoyang Wang
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9. Hui Tan
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10. Song Song
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11. Guisheng Zhang
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12. Xiaohui Zhang
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13. K. N. Houk
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14. Ning Jiao
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Corresponding authors

Correspondence to K. N. Houk or Ning Jiao.

Supplementary information

Supplementary Information

This file contains Supplementary Information (see Table of Contents in PDF for full description).

Supplementary Data

This file contains the crystal structure of 48 in Fig 3.

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Qiu, X., Sang, Y., Wu, H. et al. Cleaving arene rings for acyclic alkenylnitrile synthesis. Nature (2021). https://ift.tt/3zgWLcm

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• Received: 17 February 2021

• Accepted: 06 July 2021

• Published: 19 July 2021

• DOI: https://doi.org/10.1038/s41586-021-03801-y

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Cleaving arene rings for acyclic alkenylnitrile synthesis - Nature.com
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