Thursday, 6 October 2011

1P4: b) Synthesis of tetrasubstitutedbicyclo[3.2.1]octenes as potential inhibitors of influenza virus sialidase

P. S. Jones et al.17 synthesized several racemic  bicyclo[3.2.1]octene derivatives and evaluated as inhibitors of influenza virus sialidases. The 5-acetamido-bicyclo[3.2.1]octenol (9) showed modest activity against influenza A and B virus sialidases. The [3.2.1] bicyclic nucleus was constructed from the readily available ester (7) using an extension of the method of Rodrigues et a1.18 This method involves a base promoted Michael addition followed by an intramolecular aldol reaction and is typified by the reaction between methyl-2-oxocyclopentanecarboxylate and crotonaldehyde.18 In his work, Rodrigues18 used an aldehyde as the aldol component. Jones investigated that the carbonyl group of an α-keto-b, γ-unsaturated ester might also undergo this reaction and at the same time introduce carboxyl functionality. The required α-keto-b, γ-unsaturated ester (6) was prepared19 in 29% yield by reaction of 3-pentyl vinyl ether20 with t-butyl oxalyl chloride.21 Reaction of the α-keto-b, γ-unsaturated ester (6) with methyl 2-oxocyclopentanecarboxylate (6) in a mixture of N,N-dimethylpropylene urea and dichloromethane with DBU as base gave the product 8 as a racemic mixture of four diastereoisomers (8a-d) (Scheme 2). Jones et al prepared compound (9) from 8a in a six step. Compound (9) contains four functional group, alcoholic, carboxylic, amide and ether. Compound (9) and intermediates were tested inhibitory activity against influenza A and influenza B.









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17.  P. S. Jones, P. W. Smith, G. W. Hardy P. D. Howes, and R. C. Bethell, Bioorg. Med. Chem. Lett., 1999, 9, 605.
18.   M. Filippini, R. Faure, and J. Rodriguez, J. Org. Chem., 1995, 60, 6872.
19.  L. F. Tietze, H. Meier, and E. Voss, Synthesis, 1988, 274
20. E. Taskinen, and J. Hellman, Magn. Reson. Chem., 1994, 353.
21. L. G. Mueller, and R. G. Lawton, J. Org. Chem., 1979, 44, 4741.
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