General catalytic asymmetric routes toward cyclopentanoid and cycloheptanoid core structures embedded in numerous natural products have been developed. The central stereoselective transformation in our divergent strategies is the enantioselective decarboxylative alkylation of seven-membered β-ketoesters to form α-quaternary vinylogous esters. Recognition
Methylation of 1, 3-cyclopentanedione, 1, 3-cyclohexanedione, and 1, 3-cycloheptanedione with iodomethane in aprotic solvents in the absence and in the presence of 18-crown-6.
Sraga J and Hrnciar P.
Chemical Papers, 35(1), 119-126 (1981)
Michael additions of 1, 3-cycloalkanediones to dimethyl acety-lenedicarboxylate.
We report the large-scale synthesis of 1,3-cyclooctanedione in five steps with 29% yield. This molecule is a synthetic precurser to difluorinated cyclooctyne, which participates in a bioorthogonal copper-free click reaction with azides. The final step demonstrates the first successful application
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