Nickel-Catalyzed Sila-Cycloaddition of Dichlorodisilanes: Selective Si─Cl Activation for Cyclic Disilanes and Enantioenriched Synthesis
Dr. Liangliang Qi
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
Both authors contributed equally to this work.
Search for more papers by this authorShaojie Xu
Department of Chemistry and Materials Science, School of Science, Xi'an Jiaotong-Liverpool University, Suzhou, 215123 China
Both authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Xiaobo Pang
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorYu-Ke Wu
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
Search for more papers by this authorCorresponding Author
Prof. Xiaotai Wang
Department of Chemistry and Materials Science, School of Science, Xi'an Jiaotong-Liverpool University, Suzhou, 215123 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Prof. Xing-Zhong Shu
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorDr. Liangliang Qi
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
Both authors contributed equally to this work.
Search for more papers by this authorShaojie Xu
Department of Chemistry and Materials Science, School of Science, Xi'an Jiaotong-Liverpool University, Suzhou, 215123 China
Both authors contributed equally to this work.
Search for more papers by this authorCorresponding Author
Prof. Xiaobo Pang
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorYu-Ke Wu
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
Search for more papers by this authorCorresponding Author
Prof. Xiaotai Wang
Department of Chemistry and Materials Science, School of Science, Xi'an Jiaotong-Liverpool University, Suzhou, 215123 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorCorresponding Author
Prof. Xing-Zhong Shu
State Key Laboratory of Applied Organic Chemistry (SKLAOC) and College of Chemistry and Chemical Engineering, Lanzhou University, 222 South Tianshui Road, Lanzhou, 730000 China
E-mail: [email protected]; [email protected]; [email protected]
Search for more papers by this authorGraphical Abstract
A nickel-catalyzed [4 + 2] sila-cycloaddition between dichlorodisilanes and 1,3-dienes enables efficient access to diverse cyclic disilanes via selective Si─Cl activation. The method tolerates broad diene scope, offers an enantioselective variant, and reveals a unique Ni⁰-mediated SN2-type activation pathway.
Abstract
Disilanyl architectures holds significant value across diverse fields, particularly in the development of advanced materials. However, their limited accessibility has hindered broader exploration. Herein, we report a catalytic strategy for the synthesis of structurally diverse cyclic disilanes through a [4 + 2] sila-cycloaddition between readily available dichlorodisilanes and 1,3-dienes. This transformation proceeds under mild, reductive nickel catalysis via an unusual Si─Cl bond activation pathway and accommodates a broad range of dienes, including bulk feedstocks, cyclic, multi-substituted, aliphatic, aromatic dienes, and trienes. An asymmetric variant further enables the efficient construction of chiral disilane frameworks with high enantioselectivity. The resulting disilacarbocycle adopts boat-like conformations, as revealed by X-ray analysis, due to the elongated Si─Si and Si─C bonds. Mechanistic studies suggest that a triplet Ni0 species engages in an SN2-type oxidative addition to the Si─Cl bond, favoring this pathway over a concerted Si─Si activation. The resulting Si─Ni(I) intermediates are energetically preferred over Si─Ni(II) analogs in the subsequent diene insertion step.
Conflict of Interests
The authors declare no conflict of interest.
Open Research
Data Availability Statement
The data that support the findings of this study are available in the Supporting Information of this article.
Supporting Information
| Filename | Description |
|---|---|
| anie202509961-supp-0001-SuppMat.pdf13.8 MB | Supporting Information |
| anie202509961-supp-0002-SuppMat.zip322 KB | Supporting Information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
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