27602-79-5Relevant articles and documents
Palladium-Catalyzed Highly Regioselective Hydrocarboxylation of Alkynes with Carbon Dioxide
Chen, Pengquan,Cheng, Ruixiang,Jiang, Huanfeng,Lei, Ming,Lou, Hongming,Qi, Chaorong,Shi, Fuxing,Wang, Lu,Wu, Wanqing,Xiong, Wenfang,Zhu, Baiyao
, p. 7968 - 7978 (2020/08/21)
A Pd-catalyzed highly regioselective hydrocarboxylation of alkynes with carbon dioxide has been established. By the combination of Pd(PPh3)4 and 2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (binap), a variety of functionalized alkynes, including aryl alkynes, aliphatic alkynes, propargylamines, and propargyl ethers, could be leveraged to provide a wide array of α-acrylic acids in high yields with high regioselectivity under mild reaction conditions. Experimental and DFT mechanistic studies revealed that this reaction proceeded via the cyclopalladation process of alkynes and carbon dioxide in the presence of binap to generate a five-membered palladalactone intermediate and enabled the formation of Markovnikov adducts. Moreover, this strategy provided an effective method for the late-stage functionalization of alkyne-containing complicated molecules, including natural products and pharmaceuticals.
Structural insights into the ene-reductase synthesis of profens
Waller,Toogood,Karuppiah,Rattray,Mansell,Leys,Gardiner,Fryszkowska,Ahmed,Bandichhor,Reddy,Scrutton
, p. 4440 - 4448 (2017/07/10)
Reduction of double bonds of α,β-unsaturated carboxylic acids and esters by ene-reductases remains challenging and it typically requires activation by a second electron-withdrawing moiety, such as a halide or second carboxylate group. We showed that profen precursors, 2-arylpropenoic acids and their esters, were efficiently reduced by Old Yellow Enzymes (OYEs). The XenA and GYE enzymes showed activity towards acids, while a wider range of enzymes were active towards the equivalent methyl esters. Comparative co-crystal structural analysis of profen-bound OYEs highlighted key interactions important in determining substrate binding in a catalytically active conformation. The general utility of ene reductases for the synthesis of (R)-profens was established and this work will now drive future mutagenesis studies to screen for the production of pharmaceutically-active (S)-profens.
Cs2CO3-promoted carboxylation of N-tosylhydrazones with carbon dioxide toward α-arylacrylic acids
Sun, Song,Yu, Jin-Tao,Jiang, Yan,Cheng, Jiang
, p. 2855 - 2860 (2015/03/18)
A Cs2CO3-promoted carboxylation of N-tosylhydrazones and CO2 has been developed. The reaction proceeded efficiently at 80 C under atmospheric CO2, gave the corresponding α-arylacrylic acids in moderate to good yields. This method was featured with (1) the employment of Cs2CO3 rather than nBuLi as the base; (2) a reaction temperature of 80 C rather than -78 C.
