期刊
ACS CATALYSIS
卷 5, 期 7, 页码 4300-4308出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.5b00898
关键词
asymmetric catalysis; C-C coupling C-H activation; chiral phosphines; palladium
资金
- Ministere de l'Enseignement Superieur et de la Recherche
- Institut Universitaire de France
New binepine ligands have been synthesized, and characterized and have been shown to induce high diastereo- and enantioselectivity in the intramolecular arylation of primary and secondary C(sp(3))-H bonds, giving rise to fused cyclopentanes. The ligands were obtained as bench-stable phosphonium tetrafluoroborate salts that can be directly employed in catalysis. It was shown that a ferrocenyl P-substituent on the ligand allows achievement of high stereoselectivities in combination with potassium carbonate for the arylation of primary C-H bonds under unprecedentedly low temperature (90 degrees C) and catalyst loading (1-2 mol % Pd/2-3 mol % ligand). Using a base-free precatalyst, carbonate was shown to be the active base and to provide higher stereoselectivities than acetate and pivalate. The more difficult arylation of secondary C-H bonds could also be achieved and required fine-tuning of the ligand structure and the carbonate countercation. This method allowed generation of fused tricyclic products containing three adjacent stereocenters as single diastereoisomers and with moderate to high enantioselectivity. Experimental data indicated that the enantiodetermining C-H activation step involves a monoligated species. DFT (PBE0-D3) calculations were performed with a prototypical binepine ligand to understand the origin of the enantioselectivity. The preference for the major enantiomer was traced to the establishment of a more efficient network of weak attractive interactions between the phosphine ligand and the substrate.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据