Antiproliferating Polyquinanes. V. Di-and Triquinanes Involving α-Methylene or α-Alkylidene Cyclopentanone, Cyclopentenone, and γ-Lactone Systems

Abstract

New analogues related to quadrone (3), 3-methylenetricyclo [4.3.2.0^1.5] undecan-4-one (14), 4-methylenetricyclo [4.3.2.0^{1, 5}] undecan-3-one (15), and 2-methylenetricyclo [4.3.2.0^{1, 5}] undec-4-en-3-one (16), and novel propellane-and angular-type triquinanes, 3-methylenetricyclo [3.3.3.0] undecan-2-one (17), (E) -3-propylidene-and (E) -3- (5-carbomethoxy) pentylidenetricyclo [3.3.3.0] undecan-2-ones (18 and 19), (E) -5- (2-oxotricyclo [3. 3.3.0] undecan-3-ylidene) pentyl (E) -cinnamate (20), 2-methylenetricyclo [3.3.3.0] undecan-3-one (21), 4-methylene-2-oxatricyclo [3.3.3. 0] undecan-3-one (22), and 7-methylenetricyclo [6. 3. 0. 0, ^{1, 5}] undecan-6-one (23), were readily synthesized through skeletal transformations, and showed antiproliferating activity. Biomimetic reactions of a model compound of 3, 2-methylenetricyclo [4.3.2.0^{1, 5}] undecan-3-one (8), with propanethiol, etc. were undertaken. Correlations of the activity of some polyquinanes with second-order rate constants of addition of L-cysteine and with the carbon-13 nuclear magnetic resonance chemical shifts of exo-methylene β-carbons are discussed.