Enantio- and regioselective CpRu-catalyzed Carroll rearrangement

被引:17
作者
Austeri, Martina [1 ]
Buron, Frederic [1 ]
Constant, Samuel [1 ]
Lacour, Jerome [1 ]
Linder, David [1 ]
Mueller, Jessica [1 ]
Tortoioli, Simone [1 ]
机构
[1] Univ Geneva, Dept Organ Chem, CH-1211 Geneva 4, Switzerland
关键词
allyl complexes; enantioselective catalysis; ruthenium; N ligands; hexacoordinated phosphorus;
D O I
10.1351/pac200880050967
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The addition of unstabilized carbonyl nucleophiles to allyl-metal fragments still represents a challenge for generating stereo selectively tertiary (and quaternary) stereogenic centers. In this context, the decarboxylative Carroll rearrangement of secondary and tertiary allyl beta-ketoesters is particularly interesting since chiral gamma,delta-unsaturated ketones are obtained. Herein, we show that CpRu half-sandwich complexes can, in the presence of selected enantiopure diimine ligands, catalyze this transformation and afford complete conversions and decent level of enantiomeric excess. Zwitterionic adducts of a hexacoordinated phosphorus anion and CpRu moieties were also associated and shown to generate air-, moisture-, and microwave-stable catalysts that can be readily purified and recycled. Carroll re-arrangements of allylic beta-ketoesters performed with these zwitterionic species occur with better regio- and enantioselectivity.
引用
收藏
页码:967 / 977
页数:11
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