1393491-75-2Relevant academic research and scientific papers
Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)?H Activation
?arny, Tomá?,Baudoin, Olivier,Clemenceau, Antonin,Rocaboy, Ronan
, p. 18980 - 18984 (2020)
The 1,4-palladium shift strategy allows the functionalization of remote C?H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp3)?H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh3 as the ligand, and leads to the amide rather than the previously reported indanone product.
Diastereoselective Construction of Eight-Membered Carbocycles through Palladium-Catalyzed C(sp3)-H Functionalization
Wan, Bin,Lu, Zhuoer,Wu, Zhuo,Cheng, Cang,Zhang, Yanghui
supporting information, p. 1269 - 1274 (2021/03/03)
A palladium-catalyzed cross-coupling reaction of 2-alkylphenyl bromides with biphenylene has been developed. The reactions formed eight-membered carbocycles through C(sp3)-H activation and the formation of two C-C bonds, and the chiral products were obtai
Direct Synthesis of Cyclopropanes from gem-Dialkyl Groups through Double C-H Activation
Clemenceau, Antonin,Thesmar, Pierre,Gicquel, Maxime,Le Flohic, Alexandre,Baudoin, Olivier
supporting information, p. 15355 - 15361 (2020/10/20)
Cyclopropanes are important structural motifs found in numerous bioactive molecules, and a number of methods are available for their synthesis. However, one of the simplest cyclopropanation reactions involving the intramolecular coupling of two C-H bonds on gem-dialkyl groups has remained an elusive transformation. We demonstrate herein that this reaction is accessible using aryl bromide or triflate precursors and the 1,4-Pd shift mechanism. The use of pivalate as the base was found to be crucial to divert the mechanistic pathway toward the cyclopropane instead of the previously obtained benzocyclobutene product. Stoichiometric mechanistic studies allowed the identification of aryl- and alkylpalladium pivalates, which are in equilibrium via a five-membered palladacycle. With pivalate, a second C(sp3)-H activation leading to the four-membered palladacycle intermediate and the cyclopropane product is favored. A catalytic reaction was developed and showed a broad scope for the generation of diverse arylcyclopropanes, including valuable bicyclo[3.1.0] systems. This method was applied to a concise synthesis of lemborexant, a recently approved anti-insomnia drug.
Copper-catalyzed domino coupling reaction: An efficient method to synthesize oxindoles
Hsieh, Jen-Chieh,Cheng, An-Yi,Fu, Jun-Hao,Kang, Ting-Wei
supporting information; experimental part, p. 6404 - 6409 (2012/09/05)
An efficient and novel procedure for a copper catalyzed domino coupling reaction has been developed, which afforded various oxindoles in good to excellent yields with tolerance of various substituents. In addition, this method could be applied to synthesize horsfiline and coerulescine in few steps with high total yields. The Royal Society of Chemistry 2012.
