35524-54-0Relevant academic research and scientific papers
Successive Pd-Catalyzed Decarboxylative Cross-Couplings for the Modular Synthesis of Non-Symmetric Di-Aryl-Substituted Thiophenes
Douglas, Liam Z.,Forgione, Pat,Liu, Jiang Tian,Messina, Cynthia
, (2020)
Oligothiophenes are important organic molecules in a number of burgeoning industries as semi-conducting materials due to their extensive π-conjugation and charge transport properties. Typically, non-symmetric, di-aryl-substituted thiophenes are prepared by the successive formation of Grignards, organotin, and/or boronic acid intermediates that can be subsequently employed in cross-coupling reactions. While reliable, these approaches present synthetic difficulties due to the reactivity of organo-metallic/pseudo-metallic species, and produce considerable amounts of waste due to necessary pre-functionalization. We have developed a decarboxylative cross-coupling route as an effective strategy for the modular and less wasteful synthesis of a wide range of non-symmetric, di-arylthiophenes. This method uses a thiophene ester building block for successive decarboxylative palladium-catalyzed couplings that allows for the efficient synthesis and evaluation of the opto-electronic properties of a library of candidate semi-conductors with functional groups that could be challenging to access using previous routes.
Pd/Cu-catalyzed dual C-H bond carbonylation towards the synthesis of fluorazones
Liao, Fan,Shi, Renyi,Sha, Yuchen,Xia, Jianhui,Liao, Weilin,Lei, Aiwen
supporting information, p. 4354 - 4357 (2017/04/21)
Pd/Cu catalyzed oxidative dual C-H bond activation/carbonylation still remains a great challenge due to the generation of by-products via C-C bond formation. Herein we developed a straightforward Pd/Cu-catalyzed oxidative dual C-H bond carbonylation process to access biologically and pharmaceutically important fluorazones from easily available N-aryl pyrroles and CO. A wide range of functional groups were well tolerated in this transformation, and O2 could be utilized as the only terminal oxidant to promote the oxidative carbonylation process.
HETEROARYL INHIBITORS OF PAD4
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Paragraph 00209-00210, (2017/09/15)
The present invention provides compounds useful as inhibitors of PAD4, compositions thereof, and methods of treating PAD4-related disorders.
Regioisomeric and Substituent Effects upon the Outcome of the Reaction of 1-Borodienes with Nitrosoarene Compounds
Eberlin, Ludovic,Carboni, Bertrand,Whiting, Andrew
, p. 6574 - 6583 (2015/10/06)
A study of the reactivity of 1-borodienes with nitrosoarene compounds has been carried out showing an outcome that differs according to the hybridization state of the boron moiety. Using an sp2 boron substituent, a one-pot hetero-Diels-Alder/ring contraction cascade occurred to afford N-arylpyrroles with low to good yields depending on the electronic properties of the substituents on the borodiene, whereas an sp3 boron substituent led to the formation of stable boro-oxazines with high regioselectivity in most of the cases, in moderate to good yields. 1H and 11B NMR studies on two boro-oxazine regioisomers showed that selective deprotection can be performed. Formation of either the pyrrole or the furan derivative is pH- and regioisomer-structure-dependent. The results obtained, together with previous B3LYP calculations, support mechanistic proposals which suggest that pyrrole, or furan, formation proceeds via oxazine formation, followed by a boryl rearrangement and an intramolecular addition-elimination sequence.
Copper(II)-Catalyzed [4+1] annulation of propargylamines with N,O-acetals: Entry to the synthesis of polysubstituted pyrrole derivatives
Sakai, Norio,Hori, Hiroaki,Ogiwara, Yohei
, p. 1905 - 1909 (2015/03/18)
Described herein is the CuCl2-catalyzed [4+1] annulation of a variety of propargylamines with N,O-acetals that function as a C1 unit, leading to the production of polysubstituted pyrrole derivatives. Three important features of the N,O-acetal during the [4+1] annulation series via 5-endo-dig cyclization are described: an enolizable substituent adjacent to the central sp3-carbon is required, the central sp3-carbon displays the functions of both an electrophile and a nucleophile, and liberation of the secondary amine smoothly leads to the aromatization. A CuCl2-catalyzed [4+1] annulation of propargylamines with N,O-acetals having an ester, a ketone, and an amide moiety, leading to the facile preparation of polysubstituted pyrrole derivatives is presented. This annulation series was achieved through 5-endo-dig cyclization and subsequent aromatization in one pot.
Palladium-catalyzed decarboxylative cross-coupling reaction between heteroaromatic Carboxylic acids and Aryl halides
Bilodeau, Francois,Brochu, Marie-Christine,Guimond, Nicolas,Thesen, Kris H.,Forgione, Pat
experimental part, p. 1550 - 1560 (2010/06/12)
"Chemical Equation Presented" A full overview of the decarboxylative cross-coupling reaction between heteroaromatic carboxylic acids and aryl halides is described. This transformation employs palladium catalysts with short reaction times providing facile synthesis of aryl-substituted heteroaromatics. The effect of each reaction parameter including solvent, base, and additive employed as well as the full substrate scope of this transformation are reported. Mechanistic evidence is also disclosed that sheds light on possible reaction pathways.
N-phenylpyrrole: A kinetic, though not thermodynamic preference for dilithiation
Faigl,Schlosser
, p. 10271 - 10278 (2007/10/02)
Under appropriate conditions the clean preparation of either the α-monolithiated or the o,α-dilithiated derivative of N-phenylpyrrole is possible. In the latter case, the first deprotonation occurs at the α-position. Dimetalation is kinetically but not thermodynamically favored.
The Synthesis of Methyl 1-Aryl-2-pyrrolecarboxylates
Kiely, John S.,Huang, Suchin
, p. 1137 - 1139 (2007/10/02)
A series of alkyl 1-(aryl)-2-pyrrolecarboxylates were prepared by the condensation of the appropriate aniline with methyl tetrahydro-2,5-dimethoxy-2-furancarboxylate in refluxing acetic acid.It was found that condensation proceeds even in substituents possessing steric bulk are present in the ortho positions of the aniline.Strong electron withdrawing substituents if conjugated to the nitrogen diverts the reaction from product to unidentified tars.
Reactivity of Geometrically Fixed Vinylaziridines: Synthesis and Thermolysis of Several 3,4-Epiminocyclohexenes
Eberbach, Wolfgang,Carre, Jean Claude
, p. 563 - 586 (2007/10/02)
The aminoalcohols 13 - 16, readly accessible by aminolysis of the oxiranes 5 and 6, are transformed into the epiminocyclohexenes 17 - 20 using triphenylphosphane/tetrachloromethane as cyclisation reagent.While the N-benzyl-monocarboxylate 17 is thermally
