OXYGEN ATOM INSERTION INTO THE BENZYLIC CARBON HYDROGEN-BOND OF (R)-(-)-2-PHENYLBUTANE BY METHYL(TRIFLUOROMETHYL)DIOXIRANE - AN EFFICIENT AND MILD REGIOSELECTIVE AND STEREOSELECTIVE SYNTHESIS OF (S)-(-)-2-PHENYL-2-BUTANOL

被引:54
作者
ADAM, W
ASENSIO, G
CURCI, R
GONZALEZNUNEZ, ME
MELLO, R
机构
[1] UNIV VALENCIA,FAC PHARM,DEPT ORGAN CHEM,E-46010 VALENCIA,SPAIN
[2] UNIV BARI,DEPT CHEM,CNR,CTR MISO,I-70126 BARI,ITALY
关键词
D O I
10.1021/jo00029a030
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
The efficient conversion of (R)-(-)-2-phenylbutane [(-)-1] into (S)-(-)-2-phenyl-2-butanol [(-)-2] with high configurational retention was achieved under remarkably mild conditions by using methyl(trifluoromethyl)dioxirane (3a). The Arrhenius activation parameters were determined by using methyl(trifluoromethyl)dioxirane (3a) in solution of 1,1,1-trifluoropropanone (TFP) or methylene chloride. A significantly lower activation energy was determined for the oxyfunctionalization of (+/-)-1 by 3a in the less polar methylene chloride. An ordered transition state I is proposed for this regio- and stereoselective O atom insertion into the benzylic C-H bond of hydrocarbon (-)-1.
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页码:953 / 955
页数:3
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