Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition: Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation

Takuo Chiba; Yoshihiro Takada; Chikara Kaneko; Fumiyuki Kiuchi; Yoshisuke Tsuda

doi:10.1248/cpb.38.3317

Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition: Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation

Takuo Chiba, Yoshihiro Takada, Chikara Kaneko, Fumiyuki Kiuchi, Yoshisuke Tsuda

Research output: Contribution to journal › Article › peer-review

15 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	3317-3325
Number of pages	9
Journal	Chemical and Pharmaceutical Bulletin
Volume	38
Issue number	12
DOIs	https://doi.org/10.1248/cpb.38.3317
Publication status	Published - 1990 Jan 1
Externally published	Yes

Keywords

X-ray analysis
biradical intermediate
conformation
conformation
cyclobutane
halogenated ethylene
isoquinolone
photocycloaddition
puckered

ASJC Scopus subject areas

Chemistry(all)
Drug Discovery

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Chiba, T., Takada, Y., Kaneko, C., Kiuchi, F., & Tsuda, Y. (1990). Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition: Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation. Chemical and Pharmaceutical Bulletin, 38(12), 3317-3325. https://doi.org/10.1248/cpb.38.3317

Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition : Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation. / Chiba, Takuo; Takada, Yoshihiro; Kaneko, Chikara et al.

In: Chemical and Pharmaceutical Bulletin, Vol. 38, No. 12, 01.01.1990, p. 3317-3325.

Research output: Contribution to journal › Article › peer-review

Chiba, T, Takada, Y, Kaneko, C, Kiuchi, F & Tsuda, Y 1990, 'Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition: Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation', Chemical and Pharmaceutical Bulletin, vol. 38, no. 12, pp. 3317-3325. https://doi.org/10.1248/cpb.38.3317

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abstract = "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.",

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Cycloadditions in Syntheses. LII. Stereochemical Pathways of 1-Isoquinolone-Chloroethylene Photo [2 + 2] cycloaddition: Determination of Regio- and Stereostructures of the Products and Explanation for Their Formation

Abstract

Keywords

ASJC Scopus subject areas

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