CYCLOADDITIONS IN SYNTHESES .52. STEREOCHEMICAL PATHWAYS OF 1-ISOQUINOLONE CHLOROETHYLENE PHOTO[2+2]CYCLOADDITION - DETERMINATION OF REGIOSTRUCTURES AND STEREOSTRUCTURES OF THE PRODUCTS AND EXPLANATION FOR THEIR FORMATION

被引：17

作者：

CHIBA, T

TAKADA, Y

KANEKO, C

KIUCHI, F

TSUDA, Y

机构：

[1] TOHOKU UNIV, INST PHARMACEUT, AOBAYAMA, SENDAI 980, JAPAN

[2] KANAZAWA UNIV, FAC PHARMACEUT SCI, KANAZAWA, ISHIKAWA 920, JAPAN

来源：

CHEMICAL & PHARMACEUTICAL BULLETIN | 1990年 / 38卷 / 12期

关键词：

PHOTOCYCLOADDITION; ISOQUINOLONE; HALOGENATED ETHYLENE; X-RAY ANALYSIS; CYCLOBUTANE; CONFORMATION; PUCKERED CONFORMATION; XXXXX - LONG AUTH-KEYWORD - XXXXX; BIRADICAL INTERMEDIATE;

D O I：

10.1248/cpb.38.3317

中图分类号：

R914 [药物化学];

学科分类号：

100701 ;

摘要：

The cycloaddition of isoquinolone and its N-methyl derivative to all the chlorinated ethylenes has been studied. The structures of all of the photoadducts were determined on the basis of X-ray crystallographic analysis as well as nuclear magnetic resonance spectroscopy and it was found that the cyclobutane rings in the adducts took puckered conformation. The details of the two-step closure process via biradical intermediates are discussed and it is concluded that sigma-bond rotation prior to spin relaxation in the biradical intermediates takes a primary role in determination of the stereochemical outcome. The interesting fact that more trans products are formed from cis-dichloroethylene and more cis products from trans-dichloroethylene can also be explained in terms of the present proposal.

引用

页码：3317 / 3325

页数：9

共 19 条

[1] ORGANIC PHOTOCHEMISTRY .9. PHOTOCYCLOADDITION OF 2-CYCLOPENTENONE TO CIS-DICHLOROETHYLENE AND TRANS-DICHLOROETHYLENE - EVIDENCE FOR INITIAL ATTACK AT CARBON-3 AND ROTATIONAL EQUILIBRATION OF DIRADICAL INTERMEDIATES [J].