Stereoselective solid-state cycloadditions controlled by substrate-template preorganization

ORGN 753

Marwan William Ghosn, mwg22@georgetown.edu1, Xuefeng Mei, xm3@georgetown.edu2, Shuanglong Liu, sl246@georgetown.edu2, and Christian Wolf, cw27@georgetown.edu2. (1) Department of Chemistry, Georgetown University, 37th and O St NW, Washington, DC 20057, (2) Chemistry Department, Georgetown University, 37th and "O" St NW, Washington, DC 20057
We have found that 1,8-dipyridylnaphthalene, a simple and rigid template, can be used to preorganize unsaturated dicarboxylic acids for stereoselective solid-state photodimerization. Formation of eight hydrogen bonds in a four component co-crystal enforces face-to-face π-stacking of the olefinic substrates in a well-defined orientation. The preorganization of two fumaric acid molecules for solid-state cycloaddition leads exclusively and quantitatively to cis,trans,cis-cyclobutanetetracarboxylic acid. We aim to expand the scope of this template-assisted solid-state synthesis approach to more challenging polyunsaturated dicarboxylic acids and amides including trans,trans-muconic acid and other substrates. Progress and challenges of this ongoing work will be discussed.


Heterocycles and Aromatics, Asymmetric Reactions and Syntheses and Total Synthesis of Complex Molecules
7:00 PM-9:00 PM, Wednesday, August 19, 2009 Walter E. Washington Convention Center -- Ballroom C, Poster

8:00 PM-10:00 PM, Monday, August 17, 2009 Walter E. Washington Convention Center -- Hall D, Sci-Mix

Division of Organic Chemistry

The 238th ACS National Meeting, Washington, DC, August 16-20, 2009