An effective use of benzoic anhydride and its derivatives for the synthesis of carboxylic esters and lactones: a powerful and convenient mixed anhydride method promoted by basic catalysts.
Various carboxylic esters are obtained at room temperature in excellent yields with high chemoselectivities from nearly equimolar amounts of carboxylic acids and alcohols using 2-methyl-6-nitrobenzoic anhydride with triethylamine by the promotion of a basic catalyst such as 4-(dimethylamino)pyridine. A variety of lactones are also prepared in high yields at room temperature from the corresponding omega-hydroxycarboxylic acids with use of 2-methyl-6-nitrobenzoic anhydride in the presence of 4-(dimethylamino)pyridine. A similar reaction occurs with triethylamine when using a catalytic amount of 4-(dimethylamino)pyridine 1-oxide as an effective promoter for the intramolecular condensation reaction. These methods are successfully applied to the synthesis of erythro-aleuritic acid lactone and an eight-membered-ring lactone moiety of octalactins A and B. The efficiency of the cyclizations is compared to those of other reported lactonizations.
Shiina
Isamu
I
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan. shiina@ch.kagu.sut.ac.jp
Kubota
Mari
M
Oshiumi
Hiromi
H
Hashizume
Minako
M
D000812:Anhydrides / Q000737:chemistry*; D001565:Benzoates / Q000737:chemistry*; D002264:Carboxylic Acids / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D004952:Esters / Q000138:chemical synthesis*; D005021:Ethylamines / Q000737:chemistry; D007783:Lactones / Q000138:chemical synthesis*; D015394:Molecular Structure; D010169:Palmitic Acids / Q000737:chemistry; D011725:Pyridines / Q000737:chemistry; D013237:Stereoisomerism
C417980:4-(dimethylamine)pyridine; D000812:Anhydrides; D001565:Benzoates; D002264:Carboxylic Acids; D004952:Esters; D005021:Ethylamines; D007783:Lactones; D010169:Palmitic Acids; D011725:Pyridines; C059860:aleuritolic acid; C102988:benzoic anhydride; C016162:triethylamine