Cyclocarbonylation of Allenyl Glyoxylate Strategy to Build the Tricyclic Core of Cyclocalopin A

Org Lett. 2022 Mar 25;24(11):2242-2247. doi: 10.1021/acs.orglett.2c00625. Epub 2022 Mar 17.

Abstract

An approach for the construction of the tricyclic framework of naturally occurring cyclocalopin A is described. The establishment of the crucial intermediate α-methylene bis-γ,δ-lactone involves a [2 + 2 + 1]-cyclocarbonylation of newly introduced allenyl glyoxylate via direct methods using Mo(CO)6 or sequential reaction pathways. The sequential reaction route involved a stannylative cyclization by Pd(0) catalyst, bromination of an vinyl stannane moiety, and final cyclocarbonylation by palladium catalysis to provide the bis-γ,δ-lactone. The feasibility of forming the spiro-system by an exo-selective [4 + 2]-cycloaddition was accomplished.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Catalysis
  • Cyclization
  • Glyoxylates*
  • Lactones
  • Molecular Structure
  • Palladium*

Substances

  • Glyoxylates
  • Lactones
  • Palladium
  • glyoxylic acid