Chirality Breeding via Asymmetric Phosphination. Palladium-Catalyzed Diastereoselective Synthesis of a P-Stereogenic Phosphine

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Abstract

Methylation of the crystallographically characterized primary alkylphosphine-borane PH2Men(BH3) (3, Men = (−)-menthyl) under phase-transfer conditions, followed by deprotection, gave the secondary phosphine PH(Me)(Men) (2). Cross-coupling of 2 with PhI in the presence of NaOSiMe3 selectively gave SP-PPh(Me)(Men) (1, L) with a variety of Pd catalyst precursors, including a complex of diastereopure SP-1, trans-PdL2(Ph)(I) (6a). In this reaction, the chiral phosphine L formally acted as a ligand in catalysis of its selective self-reproduction, but 6a was partially transformed to its diastereomers, trans-Pd(SP-1)(RP-1)(Ph)(I) (6b) and trans-Pd(RP-1)2(Ph)(I) (6c), and several other intermediates were observed during catalysis.

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