Investigations on the 1,2-Hydrogen Atom Transfer Reactivity of Alkoxyl Radicals under Visible-Light-Induced Reaction Conditions

Dan Liu; Jing Zhang; Yiyun Chen

doi:10.1055/a-1300-3453

Synlett, Table of Contents

Synlett 2021; 32(04): 356-361
DOI: 10.1055/a-1300-3453

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Radicals – by Young Chinese Organic Chemists

Investigations on the 1,2-Hydrogen Atom Transfer Reactivity of Alkoxyl Radicals under Visible-Light-Induced Reaction Conditions

Dan Liu

^aState Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China

,

Jing Zhang

^aState Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China

,

Yiyun Chen∗

^aState Key Laboratory of Bioorganic and Natural Products Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, P. R. of China

^bSchool of Chemistry and Material Sciences, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, 1 Sub-lane Xiangshan, Hangzhou 310024, P. R. of China

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Abstract

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Published as part of the Cluster Radicals – by Young Chinese Organic Chemists

Abstract

The alkoxyl radicals have demonstrated superior hydrogen atom transfer reactivity in organic synthesis due to the strong oxygen–hydrogen bond dissociation energy. However, only the intermolecular hydrogen atom transfer (HAT) and intramolecular 1,5-HAT have been widely studied and synthetically utilized for C(sp³)–H functionalization. This Account summarizes our investigations on the unusual 1,2-HAT reactivity of alkoxyl radicals under visible-light-induced reaction conditions for the α-C–H functionalization. Various mechanistic investigations were discussed in this Account to address three key questions to validate the 1,2-HAT reactivity of alkoxyl radicals.

1 Introduction

2 Could Aldehydes/Ketones Be the Sole Reaction Intermediate for the α-C–H Allylation? NO

3 Is the Alkoxyl Radical Absolutely Involved in the Reaction? YES

4 Does the 1,2-HAT of Alkoxyl Radicals Irrefutably Exist? YES

5 Conclusion

Key words

alkoxyl radical - 1,2-HAT - C–H functionalization - photoredox catalysis - N-alkoxylphthalimide - N-alkoxylpyridinium salt

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References

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