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Electrochemical‐Induced Ring Transformation of Cyclic α‐( ortho ‐Iodophenyl)‐β‐oxoesters
Author(s) -
Strehl Julia,
Kahrs Christoph,
Müller Thomas,
Hilt Gerhard,
Christoffers Jens
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201905570
Subject(s) - chemistry , ring (chemistry) , moiety , aldol reaction , electrochemistry , cleavage (geology) , bond cleavage , sequence (biology) , stereochemistry , medicinal chemistry , organic chemistry , materials science , catalysis , biochemistry , electrode , fracture (geology) , composite material
Abstract Cyclic α‐( ortho ‐iodophenyl)‐β‐oxoesters were converted in a ring‐expanding transformation to furnish benzannulated cycloalkanone carboxylic esters. The reaction sequence started by electrochemical reduction of the iodoarene moiety. In a mechanistic rationale, the resulting carbanionic species was adding to the carbonyl group under formation of a strained, tricyclic benzocyclobutene intermediate, which underwent carbon–carbon bond cleavage and rearrangement of the carbon skeleton by retro‐aldol reaction. The scope of the reaction sequence was investigated by converting cyclic oxoesters with different ring sizes yielding benzocycloheptanone, ‐nonanone and ‐decanone derivatives in moderate to good yields. Furthermore, acyclic starting materials and cyclic compounds carrying additional substituents on the iodophenyl ring were submitted to this reaction sequence. The starting materials for this transformation are straightforwardly obtained by conversion of β‐oxoesters with phenyliodobis(trifluoroacetate).