Developing P-Stereogenic, Planar–Chiral P-Alkene Ligands: Monodentate, Bidentate, and Double Agostic Coordination Modes on Ru(II)

10-Phenyl-5H-dibenz[b,f]azepine (5) is synthesized by Suzuki cross coupling of the protected bromo alkene 4 with PhB(OH)2. 5 reacts with PCl3 to afford the dichlorophosphanyl-azepine 6 in >90% yield. Alkylation of 6 with 1 equiv of t-BuMgBr leads, after recrystallization in Et2O, to the diastereomerically enriched (dr > 98:2) chloride rac-7, which the crystal structure reveals to be the (pS,RP)/(pR,SP) pair. The fact that rac-7 crystallizes in the Sohncke space group P212121 opens up the possibility of a mechanical separation of the enantiomers. Methylation of rac-7 is perfectly stereoselective with inversion of configuration at the P atom to yield the new ligand rac-8 as the (R,R)/(S,S) pair. The corresponding BH3-protected diastereomer rac-9 (i.e., the (R,S)/(S,R) pair), is isolated after flash column chromatography in 73% yield. Compounds 5–9 are accessible in multigram quantities. X-ray crystal structures of Ru(II) complexes demonstrate the ambidentate nature of ligand rac-8: Complex 10 is exclusively...