A dual catalytic manifold that enables site-selective functionalization of unactivated sp³ C–O bonds in cyclic acetals with aryl and alkyl halides is reported. The reaction is triggered by an appropriate σ*–p orbital overlap prior to sp³ C–O cleavage, thus highlighting the importance of conformational flexibility in both reactivity and site selectivity. The protocol is characterized by its excellent chemoselectivity profile, thus offering new vistas for activating strong σ sp³ C–O linkages.

中文翻译：

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构象灵活性作为实现环状缩醛中未活化 sp3 C-O 键位点选择性功能化的工具

报道了一种双催化歧管，它能够用芳基和烷基卤化物对环状缩醛中未活化的sp ^{3 C-O 键进行位点选择性功能化。}该反应是由在sp ³ C-O 裂解之前适当的 σ*-p 轨道重叠触发的，因此突出了构象灵活性在反应性和位点选择性中的重要性。该协议的特点是其出色的化学选择性特征，从而为激活强σ sp ³ C-O 键提供了新的前景。