Quinoline as an\nIntramolecular Hydride Shuttle in\nthe Deoxygenative Coupling Reaction of Alcohol and the Inert Methyl\nC(sp<sup>3</sup>)–H Bond

Reported herein is the C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond-forming at an unactivated C(sp<sup>3</sup>)–H\nbond\nvia hydride transfer-initiated deoxygenative coupling reactions. Various\npolycyclic hydroquinolines were provided under metal-free conditions\nwith excellent diastereoselectivity. Mechanistic study revealed that\nquinoline served as an intramolecular hydride shuttle to achieve the\nhydride abstraction and release in order. This methodology not only\nprovides a practical strategy for direct deoxygenative coupling for\nthe C(sp<sup>3</sup>)–C(sp<sup>3</sup>) bond-forming but also\ndevelops a new reaction type involving quinoline-enabled hydride transfer.