Reversible dimerization of (+)-myrmicarin 215B.
Brønsted acid promoted reversible dimerization of myrmicarin 215B leads to formation of a new heptacyclic product, isomyrmicarin 430B, that possesses a C1,C2-trans,C2,C3-trans-substituted cyclopentane ring. Mechanistic studies illustrate that isomyrmicarin 430B arises by isomerization of isomyrmicarin 430A via fragmentation to tricyclic azafulvenium ions. Factors influencing the structure of heptacyclic isomyrmicarin products and potential relevance of this reversible vinyl pyrroloindolizine dimerization to the biosynthesis of complex myrmicarins are discussed.
Ondrus
Alison E
AE
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, USA.
Movassaghi
Mohammad
M
D000470:Alkaloids / Q000138:chemical synthesis* / Q000737:chemistry; D019281:Dimerization; D006575:Heterocyclic Compounds, 3-Ring / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D013237:Stereoisomerism
D000470:Alkaloids; D006575:Heterocyclic Compounds, 3-Ring; C542534:isomyrmicarin 430B; C512230:myrmicarin