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Bulletin of the Korean Chemical Society (BKCS)

ISSN 0253-2964(Print)
ISSN 1229-5949(Online)
Volume 15, Number 2
BKCSDE 15(2)
February 20, 1994 

Exploratory Study of Photocyclization Reactions of N-(Trimethylsilylmethylthioalkyl)phthalimides
Ung Chan Yoon*, Sang Jin Lee, Kyung Ja Lee, Sung Ju Cho, Chan Woo Lee, Patrick S. Mariano
Studies have been conducted to explore single electron transfer (SET) induced photocyclization reactions of N-(trimethylsilylmethylthioalkyl)phthalimides (alkyl=ethyl, n-propyl, n-butyl, n-pentyl, and n-hexyl). Photocyclizations occur in methanol in modest to high yields to produce cyclized products in which phthalimide carbonyl carbon is bonded to the carbon of side chain in place of the trimethylsilyl group. Mechanism for these photocyclizations involving intramolecular SET from sulfur in the α-silylmethylthioalkyl groups to the singlet excited state phthalimide moieties followed by desilylation of the intermediate α -silylmethylthio cation radicals and cyclization by radical coupling is proposed. In contrast, photoreactions of N-(trimethylsilylmethylthioalkyl)phthalimides in acetone follow different reaction routes to produce another cyclized products in which carbon-carbon bond formation takes place between the phthalimide carbonyl carbon and the carbon α to silicon and sulfur atoms via triplet carbonyl hydrogen abstraction pathway. The normal singlet SET pathway dominates this triplet process for photoreactions of these substances in methanol while the triplet process dominates the singlet SET pathway for those in acetone. The efficient and regioselective cyclization reactions observed for photolyses in methanol represent synthetically useful processes for construction of medium and large ring heterocyclic compounds.
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