Total synthesis of the cyclopeptide alkaloid abyssenine A. Application of inter- and intramolecular copper-mediated coupling reactions in organic synthesis.
The first total synthesis of the 15-membered ring cyclopeptide alkaloid abyssenine A 1 has been achieved with a longest linear sequence of 15 steps. Central to the synthetic approach was an efficient copper-mediated Ullmann coupling/Claisen rearrangement sequence allowing for both ipso and ortho functionalization of aromatic iodide 4. This sequence was used for the synthesis of the aromatic core. The synthetic utility of copper-catalyzed coupling reactions was further demonstrated to install the enamide with a concomitant straightforward macrocyclization starting from acyclic alpha-amido-omega-vinyl iodide 13.
Toumi
Mathieu
M
Institut Lavoisier de Versailles, UMR CNRS 8180, Université de Versailles Saint Quentin en Yvelines, 78035, Versailles Cedex, France.
Couty
François
F
Evano
Gwilherm
G
D000470:Alkaloids / Q000138:chemical synthesis*; D000577:Amides / Q000737:chemistry; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis*; D003300:Copper / Q000737:chemistry*; D003500:Cyclization; D006847:Hydrocarbons, Iodinated / Q000737:chemistry; D008956:Models, Chemical; D010456:Peptides, Cyclic / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000470:Alkaloids; D000577:Amides; D019086:Bridged Bicyclo Compounds, Heterocyclic; D006847:Hydrocarbons, Iodinated; D010456:Peptides, Cyclic; C526723:abyssenine A; D003300:Copper