Asymmetric organocatalysed [1,3]-sigmatropic rearrangements.
The first organocatalysed enantioselective [1,3]-sigmatropic O- to N-rearrangement reactions are presented. The reactions take place under regio- and enantioselective control, and are catalysed by cinchona alkaloids. Two reactions have been developed the first one is the rearrangement of imidates to amides, while the other rearrangement occurs from carbamates to amines via a decarboxylation. Both transformations give nitrogen protected beta-amino acid derivatives as the product. These novel asymmetric organocatalysed [1,3]-sigmatropic O- to N-rearrangement reactions provide a reliable and efficient synthetic method for obtaining enantioenriched beta-amino acid derivates in good yield from racemic starting materials.
D000577:Amides / Q000737:chemistry; D000588:Amines / Q000737:chemistry; D000596:Amino Acids / Q000138:chemical synthesis*; D002219:Carbamates / Q000737:chemistry; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D002930:Cinchona Alkaloids / Q000737:chemistry*; D003653:Decarboxylation; D007094:Imides / Q000737:chemistry; D008956:Models, Chemical; D009584:Nitrogen / Q000737:chemistry; D009942:Organometallic Compounds / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry; D013237:Stereoisomerism
D000577:Amides; D000588:Amines; D000596:Amino Acids; D002219:Carbamates; D002930:Cinchona Alkaloids; D007094:Imides; D009942:Organometallic Compounds; D009584:Nitrogen; D010100:Oxygen