ABSTRACT
The first total synthesis of (-)-crinipellin A is described. The tetraquinane core skeleton of crinipellin A was assembled through the tandem [2 + 3] cycloaddition reaction of an allenyl diazo substrate containing a cyclopentane ring in a single operation. The absolute stereochemistry was confirmed through the total synthesis.
Subject(s)
Cyclopentanes/chemistry , Diterpenes/chemical synthesis , Methane/analogs & derivatives , Azo Compounds/chemistry , Cycloaddition Reaction , Diterpenes/chemistry , Methane/chemistry , Molecular Conformation , StereoisomerismABSTRACT
Total synthesis of ceratopicanol (1) was achieved with a tandem cycloaddition reaction of allenyl diazo compound 6 via a trimethylenemethane (TMM) diyl intermediate. The TMM diyl mediated [2+3] cycloaddition reaction furnished the consecutive quaternary carbon centers and showed an unusual diastereoselectivity.
Subject(s)
Polycyclic Compounds/chemical synthesis , Azo Compounds/chemistry , Cycloaddition Reaction , Methane/analogs & derivatives , Methane/chemistry , Polycyclic Compounds/chemistry , StereoisomerismABSTRACT
A tandem reaction strategy for forming triquinanes from linear allenyl diazo compounds through an intramolecular 1,3-dipolar cycloaddition reaction of an allenyl diazo group that generates a trimethylenemethane (TMM) diyl followed by an intramolecular [2 + 3] TMM diyl cycloaddition reaction has been developed. The new tandem cycloaddition reaction is readily applicable to the synthesis of complex molecules with high versatility and efficiency.
