Photocatalytic C(sp3)-H gem-Difluoroallylation and Alkylation with Alkenes via a Base-Assisted Formal 1,2-Hydrogen Atom Transfer of Amidyl Radicals
Meifang Tang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorBingbing Feng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorYanyang Bao
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorZhongtian Xu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorChao Huang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorHanliang Zheng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorGangguo Zhu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorCorresponding Author
Yanan Wang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
E-mail: [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Zheliang Yuan
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
E-mail: [email protected]; [email protected]Search for more papers by this authorMeifang Tang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorBingbing Feng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorYanyang Bao
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorZhongtian Xu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorChao Huang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorHanliang Zheng
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorGangguo Zhu
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
Search for more papers by this authorCorresponding Author
Yanan Wang
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
E-mail: [email protected]; [email protected]Search for more papers by this authorCorresponding Author
Zheliang Yuan
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Sciences, Zhejiang Normal University, 688 Yingbin Road, Jinhua, Zhejiang, 321004 China
E-mail: [email protected]; [email protected]Search for more papers by this authorComprehensive Summary
Compared to well-established 1,5-HAT of N-centered radicals, the synthetic applications of 1,2-HAT process were scarce due to the high barrier and constrained three-membered transition state. Here, we have developed a novel C(sp3)-H gem-difluoroallylation via a base assisted formal 1,2-HAT of amidyl radicals with the reductive quenching cycle of photocatalyst. This transformation enables the efficient formation of α-aminoalkyl radicals via 1,2-HAT and showcases good functional group tolerance. Our preliminary mechanistic experiments, along with Density Functional Theory (DFT) calculations demonstrate the feasibility of 1,2-HAT of amidyl radicals, especially when assisted by a base. Furthermore, our method also succeeds in the Giese addition of electron-deficient alkenes as well as styrene.
Supporting Information
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