41003-97-8Relevant academic research and scientific papers
Elucidating the Reaction Pathway of Decarboxylation-Assisted Olefination Catalyzed by a Mononuclear Non-Heme Iron Enzyme
Yu, Cheng-Ping,Tang, Yijie,Cha, Lide,Milikisiyants, Sergey,Smirnova, Tatyana I.,Smirnov, Alex I.,Guo, Yisong,Chang, Wei-Chen
supporting information, p. 15190 - 15193 (2018/11/23)
Installation of olefins into molecules is a key transformation in organic synthesis. The recently discovered decarboxylation-assisted olefination in the biosynthesis of rhabduscin by a mononuclear non-heme iron enzyme (P.IsnB) represents a novel approach in olefin construction. This method is commonly employed in natural product biosynthesis. Herein, we demonstrate that a ferryl intermediate is used for C-H activation at the benzylic position of the substrate. We further establish that P.IsnB reactivity can be switched from olefination to hydroxylation using electron-withdrawing groups appended on the phenyl moiety of the analogues. These experimental observations imply that a pathway involving an initial C-H activation followed by a benzylic carbocation species or by electron transfer coupled β-scission is likely utilized to complete C=C bond formation.
Synthesis of Vinyl Isocyanides and Development of a Convertible Isonitrile
Spallarossa, Martina,Wang, Qian,Riva, Renata,Zhu, Jieping
supporting information, p. 1622 - 1625 (2016/05/02)
The reaction of isocyanomethylenetriphenylphosphorane, generated in situ from the corresponding phosphonium salt, with a diverse set of aldehydes afforded vinyl isocyanides in good to high yields. Excellent E-selectivity was observed for aliphatic aldehydes and 2,6-disubstituted aromatic aldehydes, whereas Z-olefins were formed predominantly with ortho-substituted aryl aldehydes. (Z)-1-Bromo-2-(2-isocyanovinyl)benzene (5l) was found to be a truly universal isonitrile since, after Ugi reaction, the resulting secondary amide unit (RNHCO-) is convertible under both acidic and basic conditions. The application of 5l in the synthesis of polyheterocycles is also illustrated.
The Conversion of Carboxylic Acids into Isonitriles via Selenium-Phenyl Selenocarbamates
Barrett, Anthony G. M.,Kwon, Hyok,Wallace, Eli M.
, p. 1760 - 1761 (2007/10/02)
Carboxylic acids are converted into isonitriles via Schmidt rearrangement of the derived acyl azides, addition of phenylselenol to the resultant isocyanate, tributylstannane reduction and dehydration.
