REGIOSELECTIVITY OF CYCLOADDITIONS OF NITRILE OXIDES AND NITRONES TO 4-METHYLENETETRAHYDROTHIOPYRANE

被引：11

作者：

FROHLICH, J

FISERA, L

SAUTER, F

FENG, Y

ERTL, P

机构：

[1] SLOVAK UNIV TECHNOL BRATISLAVA, DEPT ORGAN CHEM, BRATISLAVA 81237, SLOVAKIA

[2] VIENNA TECH UNIV, INST ORGAN CHEM, A-1060 VIENNA, AUSTRIA

[3] COMENIUS UNIV BRATISLAVA, INST CHEM, BRATISLAVA 84215, SLOVAKIA

来源：

MONATSHEFTE FUR CHEMIE | 1995年 / 126卷 / 01期

关键词：

1,3-DIPOLAR CYCLOADDITION; NITRILE OXIDES; NITRONES; 4-METHYLENE-TETRAHYDROTHIOPYRANE; SPIROTHIACYCLOHEXANE; AM1; CALCULATIONS;

D O I：

10.1007/BF00811759

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The cycloaddition of nitrile oxides and nitrones to 4-methylene-tetrahydrothiopyrane proceeds regioselectively under the formation of spiro-substituted isoxazole derivatives 4 and 9. Semiempirical calculations (AM1) were used to analyze the electronic structure of reactants, energies of products, and activation barriers leading to these products in order to rationalize this exclusive regioselectivity. It was shown that the main factor responsible for the high stereoselectivity of this reaction is not frontier orbital control, but mainly electrostatic and steric interactions. The spiro compounds 4 were cleaved by hydrogenolysis to gamma-amino-alcohols 11, which were recyclized to spiro-oxazines 12 and 13.4 and 9 as well as 12 and 13 are derivatives of novel heterocylic systems.

引用

页码：75 / 84

页数：10

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