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

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• 作者：Alberto Herrera ; Alexander Grasruck ; Frank W. HeinemannAndreas Scheurer ; Ahmed ChelouanSibylle Frieß ; Falk Seidel ; Romano Dorta
• 刊名：Organometallics
• 出版年：2017
• 出版时间：February 13, 2017
• 年：2017
• 卷：36
• 期：3
• 页码：714-720
• 全文大小：425K
• ISSN：1520-6041

文摘

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,R_P)/(pR,S_P) 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 P-coordinated, while in complex 11 two ligands bind Ru through their P donors and stabilize the 14-electron metal center with a double agostic interaction. In complex 12, the ligand coordinates in a κP,ηp>2p>-alkene bidentate fashion.