STEREOCHEMISTRY OF THIONO-THIOLO REARRANGEMENT OF PHOSPHOROTHIOIC ESTERS .2.

被引:8
作者
BRUZIK, K [1 ]
STEC, WJ [1 ]
机构
[1] POLISH ACAD SCI,CTR MOLEC & MACROMOLEC STUDIES,PL-90362 LODZ 40,POLAND
关键词
D O I
10.1021/jo00393a005
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
1-Methylbenzyl group migration proceeds with 65% retention when (R)-(+)-2-[(l-methylbenzyl)oxy]-2-thiono-5,5-dimethyl-1,3,2-dioxaphosphorinane undergoes thiono-thiolo rearrangement in acetic acid solution. This rearrangement in trifluoroacetic acid medium occurs with much lower stereospecificity (3.5%) and net inversion of configuration at the migrating carbon. Rearrangement of (R)-(-)-2-(benzyloxy-l-d)-2-thiono-5,5-dimethyl-1,3,2-dioxaphosphorinane in CF3COOH/CH2Cl2 medium proceeds with inversion of configuration (58.3%). Thesefacts are rationalized in terms of an ion-pair mechanism. The diverse stereochemistry is explained by solvation effects in the reaction medium influencing the reactivity and equilibrium between tight ion-pair, solvent-separated ion-pair, and free ions. Base hydrolysis of (S)-(-)-2-[(l-methylbenzyl)thio]-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane and (S)-(+)-2-(benzylthio-l-d)-2-oxo-5,5-dimethyl-1,3,2-dioxaphosphorinane affords (S)-(-)-lmethylbenzylthiol and (S)-(+) -benzylthiol-I -d, respectively. © 1979, American Chemical Society. All rights reserved.
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页码:4488 / 4491
页数:4
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