US EPA

8548038 

Journal Article 

anti-Tricyclo[3.1.0.02,4]hexanes. Synthesis and Reactions 

Wissner, A; Meinwald, J 

1973 

Yes 

Journal of Organic Chemistry
ISSN: 0022-3263
EISSN: 1520-6904 

38 

9 

1697-1702 

English 

10.1021/jo00949a018 

A facile synthesis of dimethyl anti-tricyelo[3.1.0.02′4]hexane-l,2-dioarboxylate (4) involving two intramolecular nucleophilic displacements is described. Thermolysis of 4 gives dimethyl cyclohexa-l,4-diene-l,2-dicarboxylate (7). Silver ion catalyzed reaction of l,2-bis(acetoxymethyl)-anti-tricyclo[3.1.0.02′4]hexane (8) also results in ring opening, giving l,2-bis(acetoxymethyl)cyclohexa-l,4-diene (10) and 2-acetoxymethyltoluene (11). Catalytic hydrogenation of 4 proceeds stereospecifically from an endo face, giving a product shown to be dimethyl bicyclo[3.1.0]hexane-l, endo-2-dicarboxylate (17). The addition of hydrogen bromide to 4 yields a pair of products shown to be the epimeric bicyclo[3.1.0]hexanes 20 and 21, in accord with expectations for stereospecific attack of bromide ion on protonated 4. © 1973, American Chemical Society. All rights reserved.