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A Stille cross-coupling reaction was developed that delivers for the first time trifluoromethyl-substituted homoallyl compounds from α-(trifluoromethyl)benzyl chlorides and allylstannanes. This reaction proceeds even with low catalyst loadings (1 mol%) via a rare CF3–Pd–π-benzyl intermediate.

Graphical abstract: Stille cross-coupling of secondary and tertiary α-(trifluoromethyl)-benzyl chlorides with allylstannanes

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