Asymmetric iridium(I)-catalyzed allylic alkylation of monosubstituted allylic substrates with phosphinooxazolines as ligands.: Isolation, characterization, and reactivity of chiral (allyl)iridium(III) complexes

被引：67

作者：

García-Yebra, C ^{[1
]}

Janssen, JP ^{[1
]}

Rominger, F ^{[1
]}

Helmchen, G ^{[1
]}

机构：

[1] Univ Heidelberg, Inst Organ Chem, D-69120 Heidelberg, Germany

来源：

ORGANOMETALLICS | 2004年 / 23卷 / 23期

关键词：

D O I：

10.1021/om0401105

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Ir-I-catalyzed allylic alkylations of linear aryl-substituted allylic acetates proceed with enantiomeric excess of up to 95% ee using bidentate phosphinooxazolines as chiral ligands. The chiral (pi-allyl)Ir-III complexes 14 and 15 have been characterized by X-ray crystal structure analysis and spectroscopic data. The stoichiometric reaction between sodium dimethyl malonate and complex 14 proceeded with nucleophilic addition at the central allylic carbon as well as ligand exchange at Ir to give the iridacyclobutane complex 16, which was fully characterized.. Complex 16 was transformed into (pi-allyl)Ir-III complexes by treatment with Lewis acid or iodine.

引用

页码：5459 / 5470

页数：12

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