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New methodology for the stereoselective synthesis of trisubstituted olefins is presented. The use of ortho‐diphenylphosphanyl benzoate (o‐DPPB) as a directing leaving group for copper‐mediated allylic substitution with Grignard reagents allowed for the stereoselective construction of a wide range of E olefins, without the need for an adjacent electron‐withdrawing group. Our modular three‐step approach...
Stereoselective hydroformylation and stereoselective conjugate addition to enoates has been achieved in a synthetic sequence employing a substrate-bound catalyst directing the o-DPPB group (o-DPPB=ortho-diphenylphosphanyl benzoate). Furthermore, a stereoselective domino process combining hydroformylation, Wittig olefination and a transition metal catalyzed hydrogenation is described.
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