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学科主题: 金属有机化学
题名: New types of soluble polymer supported bisphosphine ligands with cyclobutane backbone for Pd-catalyzed enantioselective allylic substitutions
其他题名: 可溶性高分子负载的新型含有四元环骨架的手性双磷配体在Pd催化的不对称烯丙基取代反应中的应用
作者: Zhao DB(赵东波) ; Sun J(孙杰) ; Ding KL(丁奎岭)
通讯作者: 丁奎岭
刊名: Chem.-Eur. J.
发表日期: 2004-01-01
卷: 10, 期:23, 页:5952-5963
收录类别: SCI
部门归属: 中国科学院上海有机化学研究所
英文摘要: A highly efficient and practical optical resolution of anti head-to-head racemic coumarin dimer 7 has been achieved by molecular complexation with TADDOL, (-)-8, through a hydrogen bonding interaction to afford the corresponding two enantiomers, (-)- and (+)-7, in 70 and 75% yields, respectively, with >99% ee. Starting from enantiopure (-)-7, a new type of C-2-symmetric bisphosphine ligand (S,S,S,S)-3 with a cyclobutane backbone has been synthesized in good yield by facile transformations. The asymmetric induction efficiency of these chiral bisphosphine ligands in Pd-catalyzed asymmetric allylic substitution reactions was evaluated. Under the experimental conditions, the allylic substitution products could be obtained in excellent yields (up to 99%) and enantioselectivities (up to 98.9% ee). By taking advantage of the high enantioselectivity of this catalytic reaction and the easily derivable carboxylate groups on the cyclobutane backbone of ligand (S,S,S,S)-3, a new type of analogous ligand (S,S,S,S)-4 as well as the MeO-PEG-supported soluble ligand (S,S,S,S)-5 (PEG = polyethylene glycol) have also been synthesized and utilized in asymmetric allylic substitution reactions. In particular, the MeO-PEG supported (S,S,S,S)-5b had a synergistic effect on the enantioselectivity of the reaction compared with its nonsupported precursor (S,S,S,S)-4c, affording the corresponding allylation products 14a and 14b with excellent enantioselectivities (94.6 and 97.2 % ee, respectively). Moreover, the Pd complex of (S,S,S,S)-5b could easily be recovered and recycled several times without significant loss of enantioselectivity and activity in the allylic substitution reactions.
语种: 英语
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/17779
Appears in Collections:金属有机化学国家重点实验室_期刊论文

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Recommended Citation:
Zhao DB,Sun J,Ding KL. New types of soluble polymer supported bisphosphine ligands with cyclobutane backbone for Pd-catalyzed enantioselective allylic substitutions[J]. Chem.-Eur. J.,2004,10(23):5952-5963.
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