Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroehylene Photo[2+2]cycloaddition : Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation
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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 σ-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.
- Chemical & pharmaceutical bulletin
Chemical & pharmaceutical bulletin 38(12), 3317-3325, 1990-12-25
The Pharmaceutical Society of Japan