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Synthesis 2001(8): 1133-1142
DOI: 10.1055/s-2001-15057
PAPER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Dithiane-Based Photolabile Molecular Systems

Oleg D. Mitkin, Yongqin Wan, Alexei N. Kurchan, Andrei G. Kutateladze*
Department of Chemistry and Biochemistry, University of Denver, Denver, CO 80208-2436, USA
Fax: +1(303)8712254; e-Mail: akutatel@du.edu;
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Publication History

Received 1 February 2001
Publication Date:
24 September 2004 (online)

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Abstract

Synthesis of photolabile molecular systems based on lithiodithiane addition to carbonyl compounds is described. Dithianes of the spiro structure, e. g., 2,4,8,10-tetrathiaspiro[5.5]undecane and 2,4-dithia-8,10-dioxaspiro[5.5]undecane are utilized as tethers, thus allowing for a modular approach to building a diverse set of photocleavable molecules. A variety of carbonyl compounds ranging from simple substituted benzaldehydes to formylated benzocrown ethers, carbohydrates or calixarenes are found to be suitable for this chemistry.

Key words

photolabile molecular hosts - photoinduced electron transfer - dithiane - 2,4,8,10-tetrathiaspiro[5.5]undecane - 2,4-dithia-8,10-dioxaspiro[5.5]undecane - calix[4]arene - benzocrown ether - ribofuranose - glucopyranose - galactopyranose

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The product is a mixture of diastereomers; while 1 itself is of C2 symmetry, its disubstituted derivatives have allenic-type chirality. Combined with (in general) two new stereogenic centers at former carbonyls, it accounts for four pairs of diastereomers. Due to the macromolecular nature of most of the adducts described in this paper, we did not separate the individual diastereomers (unless otherwise stated in the experimental part). Reactions of bis-lithiated 1 with symmetric ketones produced a single(racemic)product.