Synthesis of marine polyacetylenes callyberynes A-C by transition-metal-catalyzed cross-coupling reactions to sp centers.
Efficient total syntheses of the sponge-derived hydrocarbon polyacetylenes callyberynes A-C have been achieved using metal-catalyzed cross-coupling reactions of highly unsaturated 1,3-diyne fragments as the key steps, namely: Cadiot-Chodkiewicz reaction under Alami's optimized conditions (sp-sp), sequential Sonogashira reaction of a cis,cis-divinyl dihalide (sp2-sp), and Kumada-Corriu reaction of an unactivated alkyl iodide (sp3-sp). This last approach constitutes the first application of a metal-catalyzed sp3-sp Kumada-Corriu cross-coupling reaction to the synthesis of a natural product.
López
Susana
S
Departamento de Química Organica, Facultade de Química, Universidade de Santiago de Compostela, 15782 Santiago de Compostela, Spain.
Fernandez-Trillo
Francisco
F
Midón
Pilar
P
Castedo
Luis
L
Saa
Carlos
C
D000818:Animals; D002384:Catalysis; D015394:Molecular Structure; D010456:Peptides, Cyclic / Q000138:chemical synthesis* / Q000737:chemistry; D053279:Polyynes / Q000138:chemical synthesis* / Q000737:chemistry; D011161:Porifera / Q000737:chemistry*; D013237:Stereoisomerism; D028561:Transition Elements / Q000737:chemistry*
D010456:Peptides, Cyclic; D028561:Transition Elements; C516099:callyberyne B; C516098:callyberyne C; C495935:callynormine A; D053279:Polyynes