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配体加速、铜催化的伯胺有氧氧化脱氢制腈反应

Ligand-Accelerated, Copper-Catalyzed Aerobic Oxidative Dehydrogenation of Primary Amines to Nitriles.

作者信息

Li Shiyun, An Yan, Wang Lulu, Chen Yu, Huang Jun, Li Tiesen, Wen Bin, Chen Xingquan

机构信息

College of Chemical Engineering, Fuzhou University, Fuzhou 350108, China.

Qingyuan Innovation Laboratory, Quanzhou 362801, China.

出版信息

ACS Omega. 2025 Mar 12;10(11):11454-11462. doi: 10.1021/acsomega.4c11496. eCollection 2025 Mar 25.

DOI:10.1021/acsomega.4c11496
PMID:40160799
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11947809/
Abstract

A highly efficient copper-catalyzed oxidative dehydrogenation of primary amines to access nitriles has been developed. We found that DMAP was an efficient ligand for copper-catalyzed oxidation and molecular oxygen was a green oxidizing agent. This reaction exhibited excellent functional group compatibility and a broad substrate scope. Various benzylic, allylic, and aliphatic amines were selectively and effectively oxidized to the corresponding nitriles in high yields (up to 100%). The ligand DMAP not only accelerated the reaction rate but also enhanced the stability of the catalyst. The practicality of the reaction was illustrated on a gram scale, even at a lower catalyst loading and/or under bubble air conditions.

摘要

已开发出一种高效的铜催化伯胺氧化脱氢制备腈的方法。我们发现4-二甲氨基吡啶(DMAP)是铜催化氧化的有效配体,分子氧是一种绿色氧化剂。该反应具有出色的官能团兼容性和广泛的底物范围。各种苄基、烯丙基和脂肪族胺被选择性且有效地氧化为相应的腈,产率很高(高达100%)。配体DMAP不仅加快了反应速率,还提高了催化剂的稳定性。该反应的实用性在克级规模上得到了证明,即使在较低的催化剂负载量和/或鼓泡空气条件下也是如此。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/f68b61664929/ao4c11496_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/52779374072d/ao4c11496_0004.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/68a5e8c1f306/ao4c11496_0006.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/328924f97a97/ao4c11496_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/f68b61664929/ao4c11496_0008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/52779374072d/ao4c11496_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/0a8aad2bafb9/ao4c11496_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/6726f1ffb25e/ao4c11496_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/68a5e8c1f306/ao4c11496_0006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/5d9cff3122cc/ao4c11496_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/6993f99bac7a/ao4c11496_0007.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/44d8/11947809/f68b61664929/ao4c11496_0008.jpg

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Cobalt-Catalyzed Acceptorless Dehydrogenation of Primary Amines to Nitriles.
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