Converting 1,1‐Bisborylalkanes into 1,2‐Bisborylalkanes Enabled by Iron Ligand‐to‐Metal Charge Transfer (LMCT) Photocatalysis

ABSTRACT We report herein a strategy to convert 1,1‐bisborylalkanes into 1,2‐bisborylalkanes through iron ligand‐to‐metal charge transfer (LMCT) photocatalysis. Under the optimized conditions, 1,1‐bisborylalkanes undergo hydrogen atom abstraction to generate an initial radical intermediate. Subsequent radical‐induced 1,2‐boryl group migration furnishes an open‐shell species that is more stable thermodynamically. The resulting carbon‐centered radical can be intercepted by electron‐deficient alkenes, affording a range of synthetically useful 1,2‐bisborylalkanes.