1-Methoxy-8-(diphenylphosphino)triptycene (1), featuring high structural rigidity and steric bulkiness around the phosphine functionality, was synthesized as a new chiral monophosphine ligand for transition metal-catalyzed reactions. In the presence of 5–10 mol ppm (i.e., 0.0005–0.001 mol %) Pd(OAc)2 and 1 (2 equiv for Pd), Suzuki–Miyaura cross-coupling reactions of aryl bromides and arylboronic acids proceeded effectively under mild atmospheric conditions to give the corresponding biaryl compounds in a high yield. The single-crystal X-ray analysis of a Pd(II) complex of 1 revealed its coordination structure, in which two homochiral molecules form a dimer, suggesting that triptycene could provide a chiral environment for asymmetric organic transformations. In fact, optically active 1 obtained by optical resolution showed good enantioselectivity in the palladium-catalyzed asymmetric hydrosilylation of styrene, which represents, for the first time, the asymmetric catalytic activity of triptycene-based monophosphine ligands.
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