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Deconstructive Alkylation of Unstrained Cyclic Amines via Lewis Base-Boryl Radical-Enabled Spin-Center Shift
Gui-Hao Zhang1, Zhong-Ping Cai1, Tian Ye1
1Department of Chemistry, University of Science and Technology of China, Hefei, Anhui 230026, China.
None:
Deconstructive alkylation of unstrained cyclic amines is achieved through a boryl radical-enabled spin-center shift (SCS) strategy. Mechanistic studies, including control experiments and DFT calculations, support a pathway involving boryl radical addition to a carbonyl oxygen tether, followed by SCS-mediated C-N bond cleavage and ring opening, and subsequent radical trapping by alkenes. This transition-metal-free, non-redox protocol is compatible with a range of unstrained cyclic amines and alkenes, providing an efficient approach to skeletal modification of cyclic amines.
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