ORGN 231 |
| Trichloromethyl carbinols are known to afford a-substituted carboxylic acid derivatives upon treatment with base and an appropriate nucleophile. The mechanism involves an intermediate gem-dichloroepoxide that undergoes regioselective substitution with the added nucleophile. Yields are generally high, although the conditions employed (base, solvent, temperature) have a dramatic impact on reaction efficiency. We have explored the reaction of E- and Z-alkenyl trichloromethyl carbinols with oxygen and amine nucleophiles to afford g-substituted (E)-enoates with excellent diastereoselectivity. We have also investigated a novel approach to a-selenyl and a-thiocarboxylic acids. Related reactions, including a simple sequence to homologated and oxidized carbonyl compounds via reactions with trichloromethyl carbinols, will also be disclosed. |
|
New Reactions and Methodology
1:00 PM-5:00 PM, Monday, 27 March 2006 Georgia World Congress Center -- C301, Oral
Division of Organic Chemistry |