Thermal [2+2] cycloaddition reactions are symmetry-forbidden due to ground-state orbital symmetry constraints, making them challenging to achieve under non-photochemical conditions. Now a stepwise radical intramolecular thermal crossed [2+2] cycloaddition of N-(homo)allyl gem-difluoroenamines and homoallyl gem-difluorovinyl ethers has been accomplished, through tandem gem-difluoroalkenylation of N-(homo)allylamines and homoallyl alcohols with trifluoromethyl triftosylhydrazones.
- Yongquan Ning
- Rongkai Wu
- Xihe Bi