PHOTOCYCLOADDITION OF CYCLOHEX-2-ENONES TO TETRAMETHOXYETHYLENE - FORMATION OF 2,2,3,3-TETRAMETHOXY-1-OXASPIRO[3.5]NON-5-ENES

被引：16

作者：

CRUCIANI, G ^{[1
]}

RATHJEN, HJ ^{[1
]}

MARGARETHA, P ^{[1
]}

机构：

[1] UNIV HAMBURG,INST ORGAN CHEM,W-2000 HAMBURG 13,GERMANY

来源：

HELVETICA CHIMICA ACTA | 1990年 / 73卷 / 04期

关键词：

D O I：

10.1002/hlca.19900730410

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Cyclohex‐2‐enones 1a–1c undergo photocycloaddition to tetramethoxyethylene in benzene to afford 1‐oxa‐spiro[3.5]non‐5‐enes 3 in very good yields. In MeCN as solvent, higher relative amounts of bicyclo[4.2.0]octan‐2‐ones 4 are formed. Results from similar experiments with the same enones and 2,3‐dimethylbut‐2‐ene or 1,1‐dimethoxyethene indicate that the driving force for oxetane formation is a sufficiently large difference in redox potentials between Ered of the enone and Eox of the alkene. A mechanism is proposed for cycloalk‐2‐enone + alkene photocycloadditions wherein the cyclobutane adducts arise from an exciplex intermediate and the oxetanes from a subsequently formed contact ion‐pair. Copyright © 1990 Verlag GmbH & Co. KGaA, Weinheim

引用

页码：856 / 860

页数：5

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