Stereospecific Decarboxylative Allylation of Sulfones
Journal of the American Chemical Society2010Vol. 132(35), pp. 12179–12181
Citations Over TimeTop 10% of 2010 papers
Abstract
Allyl sulfonylacetic esters undergo highly stereospecific, palladium-catalyzed decarboxylative allylation. The reaction allows the stereospecific formation of tertiary homoallylic sulfones in high yield. In contrast to related reactions that proceed at -100 degrees C and require highly basic preformed organometallics, the decarboxylative coupling described herein occurs under mild nonbasic conditions and requires no stoichiometric additives. Allylation of the intermediate alpha-sulfonyl anion is more rapid than racemization, leading to a highly enantiospecific process. Density functional theory calculations indicate that the barrier for racemization is 9.9 kcal/mol, so the barrier for allylation must be <9.9 kcal/mol.
Related Papers
- → Racemization of Amino Acids in Nature(1982)73 cited
- → [9] In Vivo racemization in mammalian proteins(1984)147 cited
- → Evaluation of Fe and Ru Pincer‐Type Complexes as Catalysts for the Racemization of Secondary Benzylic Alcohols(2016)15 cited
- → Selective racemization of amino acid amides in the presence of amino acids(1986)1 cited
- → Racemization in the Coupling Reaction, Pro-Val+Pro, with the Activated Ester Methods(1973)