Rh2(S-PTTL)3TPA-a mixed-ligand dirhodium(II) catalyst for enantioselective reactions of α-alkyl-α-diazoesters

被引：53

作者：

Boruta, David T. ^{[1
]}

Dmitrenko, Olga ^{[1
]}

Yap, Glenn P. A. ^{[1
]}

Fox, Joseph M. ^{[1
]}

机构：

[1] Dept Chem & Biochem, Brown Lab, Newark, DE 19803 USA

来源：

CHEMICAL SCIENCE | 2012年 / 3卷 / 05期

基金：

美国国家科学基金会;

关键词：

C-H INSERTION; METAL CARBENE REACTIONS; CHIRAL RH(II) CATALYST; DIASTEREOSELECTIVE SYNTHESIS; ASYMMETRIC-SYNTHESIS; 4+3 CYCLOADDITION; OXIDATION-STATE; DIAZO-COMPOUNDS; CARBOXYLATES; CYCLOPROPANATION;

D O I：

10.1039/c2sc01134d

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Herein we report the synthesis of the mixed-ligand paddlewheel complex tris[N-phthaloyl-(S)-tertleucinate](triphenylacetate)dirhodium(II), Rh-2(S-PTTL)(3)TPA, the structure of which bears similarity to the chiral crown complex Rh-2(S-PTTL)(4). Rh-2(S-PTTL)(3)TPA engages substrate classes (aliphatic alkynes, silylacetylenes, alpha-olefins) that are especially challenging in intermolecular reactions of alpha-alkyl-alpha-diazoesters, and catalyzes enantioselective cyclopropanation, cyclopropenation, and indole C-H functionalization with yields and enantioselectivities that are comparable or superior to Rh-2(S-PTTL)(4). Mixing ligands on paddlewheel complexes offers a versatile handle for diversifying catalyst structure and reactivity. The results described herein illustrate how mixed-ligand catalysts can create new opportunities for the optimization of catalytic asymmetric processes.

引用

页码：1589 / 1593

页数：5

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