Total synthesis of (S)-(-)-(E)-15,16-dihydrominquartynoic acid: a highly potent anticancer agent.
The conjugated entriyne natural product, (S)-(E)-15,16-dihydrominquartynoic acid (1), is synthesized in five linear steps and 30% overall yield from the known aldehyde 11. The key step is a one-pot in situ desilylation/Cadiot-Chodkiewicz coupling reaction affording the entriyne unit. The bromoalkyne 6 with an omega-carboxylic acid group was found to undergo a copper-catalyzed cross-coupling reaction producing the desired diyne intermediate 10, while the corresponding omega-ester bromoalkyne 14 failed to couple with triethylsilylacetylene under a variety of conditions.
Gung
Benjamin W
BW
Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA. gungbw@muohio.edu
Kumi
Godwin
G
D000480:Alkynes / Q000138:chemical synthesis*; D000970:Antineoplastic Agents / Q000138:chemical synthesis*; D005231:Fatty Acids, Unsaturated / Q000138:chemical synthesis*; D015394:Molecular Structure; D053279:Polyynes
D000480:Alkynes; D000970:Antineoplastic Agents; D005231:Fatty Acids, Unsaturated; C417933:minquartynoic acid; D053279:Polyynes