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通过NiH催化的自由基接力实现未活化烯烃与C(sp)─H化合物的氢烷基化反应。

Hydroalkylation of unactivated olefins with C(sp)─H compounds enabled by NiH-catalyzed radical relay.

作者信息

Shi Jiang-Ling, Wang Youcheng, Han Yufeng, Chen Jinqi, Pu Xiaolan, Xia Ying

机构信息

West China School of Public Health and West China Fourth Hospital, West China-PUMC C.C. Chen Institute of Health, and State Key Laboratory of Biotherapy,Sichuan University, Chengdu 610041, China.

出版信息

Sci Adv. 2024 Dec 20;10(51):eads6885. doi: 10.1126/sciadv.ads6885. Epub 2024 Dec 18.

DOI:10.1126/sciadv.ads6885
PMID:39693419
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11654677/
Abstract

The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction of C(sp)─C(sp) bonds. However, such transformation has proven to be challenging for unactivated olefins, particularly when the substrates lack directing groups or acidic C(sp)─H bonds. Here, we address this challenge by merging NiH-catalyzed radical relay strategy with a HAT (hydrogen atom transfer) process. In this catalytic system, a nucleophilic alkyl radical is generated from a C(sp)─H compound in the presence of a HAT promotor, which couples with an alkyl metallic intermediate generated from the olefin substrate with a NiH catalyst to form the C(sp)─C(sp) bond. Starting from easily available materials, the reaction not only demonstrates wide functional group compatibility but also provides hydroalkylation products with regiodivergence and excellent enantioselectivity through effective catalyst control under mild conditions.

摘要

烯烃与烷烃的氢烷基化反应是构建C(sp)─C(sp)键的一种非常理想的合成转化反应。然而，事实证明，这种转化对于未活化的烯烃具有挑战性，特别是当底物缺乏导向基团或酸性C(sp)─H键时。在这里，我们通过将NiH催化的自由基接力策略与氢原子转移（HAT）过程相结合来应对这一挑战。在该催化体系中，在HAT促进剂存在下，C(sp)─H化合物生成亲核烷基自由基，该自由基与由烯烃底物和NiH催化剂生成的烷基金属中间体偶联形成C(sp)─C(sp)键。该反应从易于获得的原料出发，不仅展示了广泛的官能团兼容性，而且在温和条件下通过有效的催化剂控制提供了具有区域发散性和优异对映选择性的氢烷基化产物。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/d9d9c98d85df/sciadv.ads6885-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/7ee3fcd1eeb4/sciadv.ads6885-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/00918b0bbf4a/sciadv.ads6885-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/337c96274b1f/sciadv.ads6885-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/ea06a1b21fbb/sciadv.ads6885-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/d9d9c98d85df/sciadv.ads6885-f5.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/7ee3fcd1eeb4/sciadv.ads6885-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/00918b0bbf4a/sciadv.ads6885-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/337c96274b1f/sciadv.ads6885-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/ea06a1b21fbb/sciadv.ads6885-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/4fb7/11654677/d9d9c98d85df/sciadv.ads6885-f5.jpg

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Chem Commun (Camb). 2024 Apr 11;60(31):4206-4209. doi: 10.1039/d4cc00499j.
2
Ligand-Controlled Regiodivergent Nickel-Catalyzed Hydroaminoalkylation of Unactivated Alkenes.配体控制的未活化烯烃的区域发散性镍催化氢胺烷基化反应
J Am Chem Soc. 2024 Feb 7;146(5):3458-3470. doi: 10.1021/jacs.3c13060. Epub 2024 Jan 25.
3
Iridium-Catalyzed Enantioselective Alkene Hydroalkylation via a Heteroaryl-Directed Enolization-Decarboxylation Sequence.
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J Am Chem Soc. 2023 Nov 8;145(44):23918-23924. doi: 10.1021/jacs.3c10163. Epub 2023 Oct 25.
4
Photoinduced Efficient Catalytic α-Alkylation Reactions of Active Methylene and Methine Compounds with Nonactivated Alkenes.光诱导活性亚甲基和次甲基化合物与非活化烯烃的高效催化α-烷基化反应
J Am Chem Soc. 2023 Oct 25;145(42):23160-23166. doi: 10.1021/jacs.3c07436. Epub 2023 Oct 17.
5
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6
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J Am Chem Soc. 2023 Oct 11;145(40):22122-22134. doi: 10.1021/jacs.3c07919. Epub 2023 Sep 25.
7
Electrochemical NiH-Catalyzed C(sp )-C(sp ) Coupling of Alkyl Halides and Alkyl Alkenes.电化学镍氢催化的卤代烃与烷基烯烃的C(sp³)-C(sp²)偶联反应
Angew Chem Int Ed Engl. 2023 Oct 26;62(44):e202311941. doi: 10.1002/anie.202311941. Epub 2023 Sep 25.
8
Recent Progress in NiH-Catalyzed Linear or Branch Hydrofunctionalization of Terminal or Internal Alkenes.镍氢催化末端或内部烯烃的线性或支化氢官能化的最新进展。
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Chem Commun (Camb). 2023 Aug 1;59(62):9424-9444. doi: 10.1039/d3cc02790b.
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J Am Chem Soc. 2023 Jul 19;145(28):15456-15464. doi: 10.1021/jacs.3c03900. Epub 2023 Jun 12.