Design and Synthesis of Novel Chiral Dirhodium(II) Carboxylate Complexes for Asymmetric Cyclopropanation Reactions

被引：75
|
作者：
Adly, Frady G. [2 ]
Gardiner, Michael G. [3 ]
Ghanem, Ashraf [1 ]
机构：
[1] Univ Canberra, Dept Biomed Sci, Canberra, ACT 2601, Australia
[2] Univ Canberra, Canberra, ACT 2601, Australia
[3] Chem Univ Tasmania, Sch Phys Sci, Hobart, Tas 7001, Australia
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 10期
关键词：
asymmetric synthesis; carbenoids; chiral catalysis; cyclopropanation; rhodium; ENANTIOSELECTIVE SYNTHESIS; CATALYST; SYMMETRY; CONSTRUCTION; SUBSTITUTION; SELECTIVITY; LIGANDS;
D O I：
10.1002/chem.201504817
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
A novel approach to the design of dirhodium(II) tetracarboxylates derived from (S)-amino acid ligands is reported. The approach is founded on tailoring the steric influences of the overall catalyst structure by reducing the local symmetry of the ligand's N-heterocyclic tether. The application of the new approach has led to the uncovering of [Rh-2(S-(PTTL)-P-tert)(4)] as a new member of the dirhodium(II) family with extraordinary selectivity in cyclopropanation reactions. The stereoselectivity of [Rh-2(S-(PTTL)-P-tert)(4)] was found to be comparable to that of [Rh-2(S-PTAD)(4)] (up to >99% ee), with the extra benefit of being more synthetically accessible. Correlations based on X-ray structures to justify the observed enantioinduction are also discussed.
引用
收藏
页码：3447 / 3461
页数：15
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