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

被引：77

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

页码：3447 / 3461

页数：15

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