Oligothiophene Synthesis by a General C-H Activation Mechanism: Electrophilic Concerted Metalation-Deprotonation (eCMD)

Long Wang, Brad P. Carrow

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109 Scopus citations


Oxidative C-H/C-H coupling is a promising synthetic route for the streamlined construction of conjugated organic materials for optoelectronic applications. Broader adoption of these methods is nevertheless hindered by the need for catalysts that excel in forging core semiconductor motifs, such as ubiquitous oligothiophenes, with high efficiency in the absence of metal reagents. We report a (thioether)Pd-catalyzed oxidative coupling method for the rapid assembly of both privileged oligothiophenes and challenging hindered cases, even at low catalyst loading under Ag- A nd Cu-free conditions. A combined experimental and computational mechanistic study was undertaken to understand how a simple thioether ligand, MeS(CH2)3SO3Na, leads to such potent reactivity toward electron-rich substrates. The consensus from these data is that a concerted, base-assisted C-H cleavage transition state is operative, but thioether coordination to Pd is associated with decreased synchronicity (bond formation exceeding bond breaking) versus the "standard" concerted metalation-deprotonation (CMD) model that was formalized by Fagnou in direct arylation reactions. Enhanced positive charge buildup on the substrate results from this perturbation, which rationalizes experimental trends strongly favoring Ï-basic sites. The term electrophilic CMD (eCMD) is introduced to distinguish this mechanism from the standard model, even though both mechanisms locate in a broad concerted continuum. More O'Ferrall-Jencks analysis further suggests eCMD should be a general mechanism manifested by many metal complexes. A preliminary classification of complexes into those favoring eCMD or standard CMD is proposed, which should be informative for studies toward tunable catalyst-controlled reactivity.

Original languageEnglish (US)
Pages (from-to)6821-6836
Number of pages16
JournalACS Catalysis
Issue number8
StatePublished - Aug 2 2019

All Science Journal Classification (ASJC) codes

  • General Chemistry
  • Catalysis


  • C-H activation
  • concerted metalation-deprotonation
  • oligothiophene
  • palladium
  • thioether


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