Stereoselectivity of triplet photocycloadditions: Diene-carbonyl reactions and solvent effects

被引：64

作者：

Griesbeck, AG ^{[1
]}

Buhr, S ^{[1
]}

Fiege, M ^{[1
]}

Schmickler, H ^{[1
]}

Lex, J ^{[1
]}

机构：

[1] Univ Cologne, Inst Organ Chem, D-50939 Cologne, Germany

来源：

JOURNAL OF ORGANIC CHEMISTRY | 1998年 / 63卷 / 12期

关键词：

D O I：

10.1021/jo971767l

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The diastereoselectivity of the photocycloaddition of benzaldehyde to furan was determined (exo/endo = 212:1) and compared with the reaction of other carbonyl compounds and carbonyl analogues. These results were compared with Paterno-Buchi reactions of cycloalkenes and cyclic enol ethers. An increase in steric demand of the a-substituent in benzoyl compounds led to a change in exo/endo-selectivity for furan cycloadditions that was not observed for cycloalkenes or cyclic enol ethers. Different ISC-reactive conformers with enhanced spin-orbit coupling are postulated as a reasonable explanation for the stereoselectivities observed. Additionally, solvent effects were studied, demonstrating the influence of photoinduced electron-transfer steps on the regio- and diastereoselectivity of Paterno-Buchi reactions with 2,3-dihydrofuran in polar solvents. Two bicyclic oxetanes (8 and 10) were characterized by X-ray structure analysis.

引用

页码：3847 / 3854

页数：8

共 80 条

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