1571-13-7Relevant articles and documents
Novel functionalized indigo derivatives for organic electronics
Klimovich, Irina V.,Zhilenkov, Alexander V.,Кuznetsova, Lidiya I.,Frolova, Lubov A.,Yamilova, Olga R.,Troyanov, Sergey I.,Lyssenko, Konstantin A.,Troshin, Pavel A.
, (2020/11/24)
A series of nine novel indigo derivatives, including diiodoindigo, octahalogenated indigoids and compounds with extended π-conjugated system, were synthesized, characterized and investigated as semiconductor materials in organic field-effect transistors (OFETs). Among them, 6,6′-diiodoindigo demonstrated the ambipolar behavior with balanced p-type and n-type mobilities. The complete substitution of hydrogens at the indigo core with halogen atoms led to low electron mobilities in OFETs. An extension of the conjugated system through the introduction of small aromatic substituents (thiophene and phenyl) resulted in predominant p-type behavior. Fusion of aromatic rings resulted in z-shaped dibenzoindigo, which showed poor charge transport properties due to the non-optimal arrangement of molecules along each other in the crystal lattice. The acquired data fulfilled the previously reported model based on the relationship between the chemical nature of substituents and their positions at the indigo core, optoelectronic properties of materials and their performance in OFETs. The results of this study will be useful for rational design of a new generation of the indigo-based semiconductors for biocompatible organic electronics.
Mechanistic Studies on the Organocatalytic α-Chlorination of Aldehydes: The Role and Nature of Off-Cycle Intermediates
Ponath, Sebastian,Menger, Martina,Grothues, Lydia,Weber, Manuela,Lentz, Dieter,Strohmann, Carsten,Christmann, Mathias
supporting information, p. 11683 - 11687 (2018/09/10)
Herein we report the isolation and characterization of aminal intermediates in the organocatalytic α-chlorination of aldehydes. These species are stable covalent ternary adducts of the substrate, the catalyst and the chlorinating reagent. NMR-assisted kinetic studies and isotopic labeling experiments with the isolated intermediate did not support its involvement in downstream stereoselective processes as proposed by Blackmond. By tuning the reactivity of the chlorinating reagent, we were able to suppress the accumulation of rate-limiting off-cycle intermediates. As a result, an efficient and highly enantioselective catalytic system with a broad functional group tolerance was developed.
Decarboxylative Alkynylation
Smith, Joel M.,Qin, Tian,Merchant, Rohan R.,Edwards, Jacob T.,Malins, Lara R.,Liu, Zhiqing,Che, Guanda,Shen, Zichao,Shaw, Scott A.,Eastgate, Martin D.,Baran, Phil S.
supporting information, p. 11906 - 11910 (2017/09/06)
The development of a new decarboxylative cross-coupling method that affords terminal and substituted alkynes from various carboxylic acids is described using both nickel- and iron-based catalysts. The use of N-hydroxytetrachlorophthalimide (TCNHPI) esters is crucial to the success of the transformation, and the reaction is amenable to in situ carboxylic acid activation. Additionally, an inexpensive, commercially available alkyne source is employed in this formal homologation process that serves as a surrogate for other well-established alkyne syntheses. The reaction is operationally simple and broad in scope while providing succinct and scalable avenues to previously reported synthetic intermediates.
