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A copper‐catalyzed regio‐ and enantioselective hydroallylation of 1‐trifluoromethylseleno (SeCF 3 )‐alkenes with hydrosilanes and allylic halides has been developed. The in situ generated copper hydride catalyst enabled access to untrivial aliphatic SeCF 3 ‐containing molecules, including substrates derived from bioactive scaffolds. Furthermore, the use of a chiral ( S )‐H 8 ‐BINAP ligand successfully induced point chirality at the α‐SeCF 3 carbon center. The enantiopurity of the products was found to be highly dependent on the leaving group of the allylic electrophile employed, with allylic bromides affording significantly enhanced enantioselectivity. To the best of our knowledge, this transformation represents the first example of asymmetric C(sp 3 )─C(sp 3 ) bond formation at the α‐position to a SeCF 3 group, a structurally underexplored yet potentially valuable motif in drug design.
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Matsui et al. (2026) studied this question.
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