ORGN 413 |
Controlling stereochemistry of addition of 5-substituted 1,3-dithianyl anions to carbonyl compounds
| Andrei G. Kutateladze and Zaiguo Li. Department of Chemistry and Biochemistry, University of Denver, 2190 E. Iliff Ave., F.W. Olin Hall, rm.202, Denver, CO 80208-2436 |
We are developing a general strategy for assembly and photoinduced disassembly of modular photolabile molecular objects, designed for applications in chemical biology. At the core of this approach is the recently discovered photofragmentation in dithiane- or trithiane-carbonyl adducts. Successful implementation of this methodology requires a systematic search for photolabile tethers capable of efficient photoinduced fragmentation and at the same time outfitted with functional groups suitable for interconnecting the desired modules in a straightforward manner. For this purpose, we synthesized several novel 1,3-dithianes that carry nucleophilic groups as "handles" in position 5 of the dithiane ring. Addition of 5-substituted dithianyl anions to carbonyl compounds normally produces trans-adducts. In this paper we report that the presence of a nucleophilic moiety, for example hydroxymethyl group (see scheme below), in position 5 affects the stereoselectivity of the reaction, with the trans/cis ratio being controlled by the addition of HMPA. A detailed experimental and computational (density functional) study will be presented. |
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Physical Organic, Materials, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Tuesday, September 9, 2003 Hilton New York -- Americas Hall 1, Poster
Division of Organic Chemistry
The 226th ACS National Meeting, New York, NY, September 7-11, 2003
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