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Oxaenediynes through the Nicholas‐Type Macrocyclization Approach
Author(s) -
Lyapunova Anna G.,
Danilkitalia A.,
Khlebnikov Alexander F.,
Köberle Beate,
Bräse Stefan,
Balova Irina A.
Publication year - 2016
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201600767
Subject(s) - chemistry , sonogashira coupling , benzothiophene , reactivity (psychology) , electrophile , stereochemistry , combinatorial chemistry , alkyne , organic chemistry , catalysis , palladium , thiophene , medicine , alternative medicine , pathology
The Nicholas‐type macrocyclization has been used for the first time for the synthesis of 10‐ and 11‐membered oxaenediynes fused to a benzothiophene. The acyclic starting materials were easily synthesized by electrophilic cyclization of o ‐(buta‐1,3‐diynyl)thioanisoles followed by a Sonogashira coupling of the resulting 2‐ethynyl‐3‐iodobenzothiophenes with functionalized alkynes. A high reactivity of the 10‐membered oxacycles in the Bergman cyclization was predicted by DFT calculations and confirmed by differential scanning calorimetry. The ability of enediynes to induce single‐strand PM2 DNA scissions was also found.