Premium
Intramolecular Reactions of Tethered Furan‐Based Bis( p ‐quinodimethanes)
Author(s) -
Klumpp Douglas A.,
Gilbert Thomas M.,
Trahanovsky Walter S.
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.201600995
Subject(s) - flash vacuum pyrolysis , chemistry , furan , diradical , intramolecular force , computational chemistry , medicinal chemistry , ab initio , photochemistry , pyrolysis , organic chemistry , singlet state , physics , nuclear physics , excited state
Tethered bis‐2,5‐dimethylene‐2,5‐dihydrofurans were generated in the gas phase by flash vacuum pyrolysis (FVP) of diester precursors. These furan‐based bis( p ‐quinodimethanes) are shown to undergo reactions leading to macrocycles. The observed products strongly support a mechanism involving cyclic diradical intermediates. Formation of the furan‐based p ‐quinodimethane and the corresponding cyclization chemistry was studied by high‐level ab initio calculations. The theoretical studies reveal the importance of the entropy‐driven elimination steps in the high‐temperature FVP chemistry.