Diastereoselective syntheses of deoxydysibetaine, dysibetaine, and its 4-epimer.
(+/-)-Deoxydysibetaine 2 and 4-epi-dysibetaine 3 were prepared in a few steps from methyl pyroglutamate through a regioselective Mannich reaction at C-2. Natural (2S,4S)-dysibetaine 1, a sponge metabolite isolated from Dysidea herbacea, and (2S)-2 were synthesized from enantiopure (S)-pyroglutaminol with very high stereoselectivity. The key steps were an original formation of stereogenic quaternary center C-2 and the diastereoselective hydroxylation at C-4.
Langlois
Nicole
N
Institut de Chimie des Substances Naturelles, CNRS, 91198 Gif-sur-Yvette, France. nicole.langlois@icsn.cnrs-gif.fr
Le Nguyen
Bao K
BK
D000818:Animals; D002384:Catalysis; D047088:Dysidea / Q000737:chemistry*; D015394:Molecular Structure; D019906:Nuclear Magnetic Resonance, Biomolecular; D011758:Pyrroles / Q000737:chemistry; D011760:Pyrrolidinones / Q000138:chemical synthesis* / Q000737:chemistry; D011761:Pyrrolidonecarboxylic Acid / Q000031:analogs & derivatives* / Q000737:chemistry*; D013237:Stereoisomerism
D011758:Pyrroles; D011760:Pyrrolidinones; C431075:dysibetaine; C431590:pyroglutaminol; D011761:Pyrrolidonecarboxylic Acid