Abstract
Heteroaromatic bases, such as lepidine, phenanthridine, isoquinoline, etc., were treated with cycloalkanes, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc., under warming conditions with benzoyl peroxide (BPO) to form heteroaromatic bases bearing cycloalkyl groups in good yields. Here, the inert C(sp3)‐H bond of cycloalkanes could be functionalized to C(sp3)‐heteroaromatic bases via an oxidative radical reaction pathway under transition‐metal‐free conditions.

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