Developing catalytic enantioselective fluorination

被引：0

作者：

Togni, A ^{[1
]}

Mezzetti, A ^{[1
]}

Barthazy, P ^{[1
]}

Becker, C ^{[1
]}

Devillers, I ^{[1
]}

Frantz, R ^{[1
]}

Hintermann, L ^{[1
]}

Perseghini, M ^{[1
]}

Sanna, M ^{[1
]}

机构：

[1] ETH Honggerberg, Swiss Fed Inst Technol, Dept Chem, ETH Zurich, CH-8093 Zurich, Switzerland

来源：

CHIMIA | 2001年 / 55卷 / 10期

关键词：

asymmetric catalysis; enantioselective chlorination; enantioselective fluorination; ruthenium fluoro complexes; titanium TADDOLato complexes;

D O I：

暂无

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The background that led to the development of the first catalytic and enantioselective carbon-fluorine bond-forming reaction is presented. Two different approaches, i.e. the use of nucleophilic and electrophilic fluorinating agents, respectively, have been pursued. Well-defined Ru(II) 16-electron systems of the type [RuF(PP)(2)](+) (where PP is a chelating diphosphine), as well as analogous complexes containing tetradentate PNNP ligands, were found to catalyze the halogen exchange reaction of activated alkyl chlorides, bromides, and iodides in the presence of TIF as the fluorine source. Isolable crystalline [TiCl2(TADDOLato)] complexes are efficient catalysts in the enantioselective fluorination of 2-substituted 1,3-dicarbonyl compounds with Selectfluor((R)) (also called F-TEDA; 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis[tetrafluoroborate]). Levels of enantioselectivity up to 90% ee were obtained.

引用

页码：801 / 805

页数：5

共 51 条

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