Premium
Post‐Cycloaddition–Retroelectrocyclization Transformations of Polycyanobutadienes
Author(s) -
Lacy Adam R.,
Vogt Anna,
Boudon Corinne,
Gisselbrecht JeanPaul,
Schweizer W. Bernd,
Diederich François
Publication year - 2013
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.201201371
Subject(s) - chemistry , cycloaddition , cyclic voltammetry , aniline , electrochemistry , naphthalene , chromophore , medicinal chemistry , photochemistry , combinatorial chemistry , organic chemistry , electrode , catalysis
The thermal [2+2] cycloaddition–retroelectrocyclization (CA‐RE) reaction between a range of alkynes, activated by electron‐donating anilino ( p ‐H 2 NC 6 H 4 ‐) substituents, and the electron‐deficient olefins tetracyanoethene (TCNE) and 7,7,8,8‐tetracyano‐ p ‐quinodimethane (TCNQ) delivered anilino‐substituted polycyanobutadienes (PCBDs). The aniline NH 2 groups provide a convenient handle for further transformations, yielding a new series of PCBDs without an electron‐donating group. Electrochemical investigations by rotating disk voltammetry and cyclic voltammetry revealed large anodic shifts in both the first and second reduction potentials as a result of the removal of the electron‐donating functionality. This methodology allows for PCBD‐containing substrates to be further elaborated, generating a new family of chromophores previously inaccessible by alternative synthetic methods.