Metal-catalyzed 1,2-shift of diverse migrating groups in allenyl systems as a new paradigm toward densely functionalized heterocycles.

ABSTRACT: A general, mild, and efficient 1,2-migration/cycloisomerization methodology toward multisubstituted 3-thio-, seleno-, halo-, aryl-, and alkyl-furans and pyrroles, as well as fused heterocycles, valuable building blocks for synthetic chemistry, has been developed. Moreover, regiodivergent conditions have been identified for C-4 bromo- and thio-substituted allenones and alkynones for the assembly of regioisomeric 2-hetero substituted furans selectively. It was demonstrated that, depending on reaction conditions, ambident substrates can be selectively transformed into furan products, as well as undergo selective 6-exo-dig or Nazarov cyclizations. Our mechanistic investigations have revealed that the transformation proceeds via allenylcarbonyl or allenylimine intermediates followed by 1,2-grou

SUBMITTER: Dudnik AS 

PROVIDER: S-EPMC3686647 | biostudies-literature | 2008 Jan

REPOSITORIES: biostudies-literature