A Metal-Free and Redox-Neutral Benzylic C-O Cyclization for Succinct Access of Helical Chromenes

A redox-neutral benzylic C-O cyclization under beneficial transition-metal-free conditions is reported. Key to the success of this process is the utilization of the Tf anion as the leaving group for achieving the redox-neutral transformation. This protocol delivers a series of captivating helical compounds having various functionality in good-to-excellent yields. It is particularly noteworthy that sterically hindered helical compounds are conformationally stable. In addition to simple helical chromenes, the bihelical multiple-ring systems which are potentially useful in material chemistry are also easily attained by employing this method. DFT calculation revealed that quinone intermediate is the key species, among four possible mechanisms, for accomplishing the desired cyclization via an oxa-6 pi-electrocyclization pathway.

Automated summary

This study reports a redox-neutral benzylic C-O cyclization under transition-metal-free conditions utilizing the Tf anion as the leaving group. The protocol delivers a series of captivating helical compounds with various functionality in good-to-excellent yields. It is particularly notable that sterically hindered helical compounds are conformationally stable. In addition, bihelical multiple-ring systems potentially useful in material chemistry can also be easily obtained using this method.