50266-60-9Relevant articles and documents
A direct route to polythiophenes displaying lateral substituents: Easy one-step synthesis and polymerization of thiophene monomers substituted by a dimethylenecarboxylate (CH2CH2COOR) appendage on the 3-position
Sengmany, Stephane,Ceballos, Claire,Belhadj, Romain,Cachet-Vivier, Christine,Gall, Erwan Le,Brissault, Blandine,Penelle, Jacques,Leonel, Eric
, p. 900 - 911 (2012)
Thiophene monomers displaying a dimethylenecarboxylate (CH 2CH2COOR) substituent on the 3-position of the aromatic ring can be easily obtained and in one step from the electrochemically induced reaction of 3-bromothiophene with the corresponding acrylate (CH 2=CHCOOR). The synthesis of the ethyl ester monomer, of related 2,5-dihalogenothiophenes, and their polymerization are reported. Despite the surprisingly low solubilities displayed by the polymers, a full spectroscopic characterization could be performed and the data fully analyzed. Oxidative polymerizations (FeCl3 or electropolymerization) yield a regioirregular polythiophene, with 60-70% of head-to-tail diads. Both experimental and theoretical results suggest that the nonconjugated ester plays a very minor role-if any-in the polymerizations under oxidative conditions, but has a significant influence on the polymer properties. Preliminary attempts to polymerize the dihalogenothiophenes under reductive conditions were hampered by the even lower solubilities exhibited by the regioregular oligomers.
Synergistic Relay Reactions To Achieve Redox-Neutral α-Alkylations of Olefinic Alcohols with Ruthenium(II) Catalysis
Kan, Jian,Li, Chao-Jun,Li, Chen-Chen,Li, Jianbin,Lv, Leiyang,Qiu, Zihang
supporting information, p. 4544 - 4549 (2020/02/04)
Herein, we report a ruthenium-catalyzed redox-neutral α-alkylation of unsaturated alcohols based on a synergistic relay process involving olefin isomerization (chain walking) and umpolung hydrazone addition, which takes advantage of the interaction between the two rather inefficient individual reaction steps to enable an efficient overall process. This transformation shows the compatibility of hydrazone-type “carbanions” and active protons in a one-pot reaction, and at the same time achieves the first Grignard-type nucleophilic addition using olefinic alcohols as latent carbonyl groups, providing a higher yield of the corresponding secondary alcohol than the classical hydrazone addition to aldehydes does. A broad scope of unsaturated alcohols and hydrazones, including some complex structures, can be successfully employed in this reaction, which shows the versatility of this approach and its suitability as an alternative, efficient means for the generation of secondary and tertiary alcohols.
Asymmetric Synthesis of γ-Amino Alcohols by Copper-Catalyzed Hydroamination
Ichikawa, Saki,Buchwald, Stephen L.
supporting information, p. 8736 - 8739 (2019/11/03)
Asymmetric synthesis of γ-amino alcohols from unprotected allylic alcohols by a copper-catalyzed hydroamination strategy has been developed. Using easily accessible starting materials, a range of chiral 1,3-amino alcohols were prepared with excellent regio- and enantioselectivity. Further, this protocol provided an efficient one-step method for the enantioselective synthesis of γ-amino alcohols in an intermolecular manner.
