Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core

N.A. Danilkina, A.E. Kulyashova, A.F. Khlebnikov, S. Bräse, I.A. Balova

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41 Citations (Scopus)

Abstract

An 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.
Original languageEnglish
Pages (from-to)9018-9045
Number of pages28
JournalJournal of Organic Chemistry
Volume79
Issue number19
DOIs
Publication statusPublished - 2014

Cite this

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title = "Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core",
abstract = "An efficient strategy for the synthesis of asymmetricallysubstituted enediynes fused to benzothiophene, benzofuran,and indole was developed. The proposed approach is based on theelectrophilic 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 of2-ethynyl-3-iodoheteroindenes. These substrates and their modifiedderivatives were easily converted by Sonogashira coupling with acetylenesto a variety of asymmetrically substituted acyclic enediynesfused to heterocycles. The tolerance of the developed methodologyto a variety of functional groups is a great advantage in the synthesisof macrocyclic enediyne systems fused to a heterocyclic core. Synthesisof indole-fused 12-membered macrocyclic dienediyne was achievedusing ring-closing metathesis as a key step.",
author = "N.A. Danilkina and A.E. Kulyashova and A.F. Khlebnikov and S. Br{\"a}se and I.A. Balova",
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TY - JOUR

T1 - Electrophilic Cyclization of Aryldiacetylenes in the Synthesis of Functionalized Enediynes Fused to a Heterocyclic Core

AU - Danilkina, N.A.

AU - Kulyashova, A.E.

AU - Khlebnikov, A.F.

AU - Bräse, S.

AU - Balova, I.A.

PY - 2014

Y1 - 2014

N2 - An efficient strategy for the synthesis of asymmetricallysubstituted enediynes fused to benzothiophene, benzofuran,and indole was developed. The proposed approach is based on theelectrophilic 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 of2-ethynyl-3-iodoheteroindenes. These substrates and their modifiedderivatives were easily converted by Sonogashira coupling with acetylenesto a variety of asymmetrically substituted acyclic enediynesfused to heterocycles. The tolerance of the developed methodologyto a variety of functional groups is a great advantage in the synthesisof macrocyclic enediyne systems fused to a heterocyclic core. Synthesisof indole-fused 12-membered macrocyclic dienediyne was achievedusing ring-closing metathesis as a key step.

AB - An efficient strategy for the synthesis of asymmetricallysubstituted enediynes fused to benzothiophene, benzofuran,and indole was developed. The proposed approach is based on theelectrophilic 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 of2-ethynyl-3-iodoheteroindenes. These substrates and their modifiedderivatives were easily converted by Sonogashira coupling with acetylenesto a variety of asymmetrically substituted acyclic enediynesfused to heterocycles. The tolerance of the developed methodologyto a variety of functional groups is a great advantage in the synthesisof macrocyclic enediyne systems fused to a heterocyclic core. Synthesisof indole-fused 12-membered macrocyclic dienediyne was achievedusing ring-closing metathesis as a key step.

U2 - 0.1021/jo501396s

DO - 0.1021/jo501396s

M3 - Article

VL - 79

SP - 9018

EP - 9045

JO - Journal of Organic Chemistry

JF - Journal of Organic Chemistry

SN - 0022-3263

IS - 19

ER -