115382-34-8Relevant articles and documents
Regio- and Stereoselective Synthesis of (Z)-3-Ylidenephthalides via H3PMo12O40-Catalyzed Cyclization of 2-Acylbenzoic Acids with Benzylic Alcohols
Yang, Guoping,Li, Ke,Lin, Xiaoling,Li, Yijin,Cui, Chengxing,Li, Shixiong,Cheng, Yuanyuan,Liu, Yufeng
supporting information, p. 3017 - 3022 (2021/09/13)
We report an exclusively tandem C—O and C—C bond forming beyond the esterification and cyclization reaction of 2-acylbenzoic acids with alcohols to regio- and stereoselective synthesis of the (Z)-3-ylidenephthalides. The reaction uses the nontoxic, inexpensive H3PMo12O40 as catalyst and produces water as the sole by-product, making the reaction environmentally benign and sustainable. Moreover, this reaction features an eco-friendly reaction condition, facile scalability, and easy derivatization of the products to drugs and bioactive compounds. The mechanism studies and density functional theory calculations reveal that the appropriate acid catalyst is the key to the selectivity of this transformation.
Cobalt-catalyzed methoxycarbonylation of substituted dichlorobenzenes as an example of a facile radical anion nucleophilic substitution in chloroarenes
Khaibulova, Tatyana S.,Boyarskaya, Irina A.,Larionov, Evgeny,Boyarskiy, Vadim P.
, p. 5876 - 5897 (2014/06/10)
A thorough mechanistic study on cobalt-catalysed direct methoxycarbonylation reactions of chlorobenzenes in the presence of methyl oxirane on a wide range of substrates, including poly-and monochloro derivatives with multiple substituents, is reported. The results demonstrate that the reaction is potentially useful as it proceeds under very mild conditions (t = 62 °C, PCO = 1 bar) and converts aryl chlorides to far more valuable products (especially ortho-substituted benzoic acids and esters) in high yields. This transformation also offers another opportunity for the utilization of environmentally harmful polychlorinated benzenes and biphenyls (PCBs). This study is the first to discover an unexpected universal positive ortho-effect: the proximity of any substituent (including Me, Ph, and MeO groups and halogen atoms) to the reaction centre accelerates the methoxycarbonylation in chlorobenzenes. The effect of the ortho-substituents is discussed in detail and explained in terms of a radical anion reaction mechanism. The advantages of the methoxycarbonylation as a model for the mechanistic study of radical anion reactions are also illustrated.
Lithiation of 2-(chloroaryl)-2-methyl-1,3-dioxolanes and application in synthesis of new ortho-functionalized acetophenone derivatives
Lukács, Gyula,Porcs-Makkay, Márta,Simig, Gyula
, p. 3211 - 3214 (2007/10/03)
2-(4-Chlorophenyl)-2-methyl-1,3-dioxolane 2a was lithiated ortho to the ketal group by treatment with butyllithium in THF at 0°C. Related 2-aryl-2-methyl-1,3-dioxolanes possessing a chlorine substituent at the meta position of the aryl group 2b,c were lithiated with butyllithium in THF at -78°C at the position between the two directing groups. The lithio species thus generated were treated with various electrophiles to give ortho-functionalized acetophenone derivatives.