4-Aryloxybutenolides As “Chiral Aldehyde” Equivalents: An Efficient Enantioselective Synthesis of (+)-Brefeldin A
Citations Over TimeTop 10% of 2002 papers
Abstract
4-(2'-Naphthoxy)-2-butenolide, readily available with high enantiopurity by a dynamic kinetic asymmetric transformation (DYKAT) of racemic 4-acyloxybutenolides (available in two steps from furfural), serves as an excellent chiral building block where the naphthoxy group strongly directs the stereochemistry of cycloadditions to the double bond. Notably, the cycloadditions of trimethylenemethanepalladium intermediates which do not exhibit good diastereoselectivity in additions to acceptors that possess many common and important chiral auxiliaries undergo cycloadditions with excellent regio- and stereocontrol. The utility of this process set the stage for an efficient new synthesis of (+)-brefeldin A, a compound of growing pharmacological significance. This synthesis also highlights the Pd-catalyzed DYKAT of crotyl carbonate to create the remote stereocenter. A new two-step method to convert aldehydes to delta-hydroxy-E-alpha,beta-enoates is also outlined.
Related Papers
- → Novel blockade by brefeldin A of intracellular transport of secretory proteins in cultured rat hepatocytes.(1986)854 cited
- → Recent developments in enantioselective iron-catalyzed transformations(2019)58 cited
- → Methods of Asymmetric Synthesis—Enantioselective Catalytic Hydrogenation(1971)142 cited
- → Brefeldin A arrests the intracellular transport of a precursor of complement C3 before its conversion site in rat hepatocytes(1987)108 cited
- → Chiral B(III) Lewis Acids(2000)19 cited