jo501396s_si_003.cif (42.63 kB)
Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core
dataset
posted on 2014-10-03, 00:00 authored by N. A. Danilkina, A. E. Kulyashova, A. F. Khlebnikov, S. Bräse, I. A. BalovaAn
efficient strategy for the synthesis of asymmetrically substituted
enediynes fused to benzothiophene, benzofuran, and indole was developed.
The proposed approach is based on the electrophilic cyclization of
diacetylenes and Sonogashira coupling. Thus, iodocyclization of readily
available ortho-functionalized (buta-1,3-diynyl)arenes
was used as a direct way for the synthesis of 2-ethynyl-3-iodoheteroindenes.
These substrates and their modified derivatives were easily converted
by Sonogashira coupling with acetylenes to a variety of asymmetrically
substituted acyclic enediynes fused to heterocycles. The tolerance
of the developed methodology to a variety of functional groups is
a great advantage in the synthesis of macrocyclic enediyne systems
fused to a heterocyclic core. Synthesis of indole-fused 12-membered
macrocyclic dienediyne was achieved using ring-closing metathesis
as a key step.