80-30-8Relevant articles and documents
Tosylamidation of Cyclohexane by a Cytochrome P-450 Model
Breslow, Ronald,Gellman, Samuel H.
, p. 1400 - 1401 (1982)
Reaction of cyclohexane with (tosyliminoiodo)benzene and manganese(III)- or iron(III)-tetraphenylporphyrin chloride affords N-cyclohexyltoluene-p-sulphonamide.
Direct Synthesis of α-Amino Nitriles from Sulfonamides via Base-Mediated C-H Cyanation
Shi, Shasha,Yang, Xianyu,Tang, Man,Hu, Jiefeng,Loh, Teck-Peng
, p. 4018 - 4022 (2021/05/26)
Herein, we disclose a transition-metal-free reaction system that enables α-cyanation of sulfonamides through C-H bond cleavage for the preparation of α-amino nitriles, including difficult-to-access all-alkyl α-tertiary scaffolds. More than 50 substrate examples prove a wide functional group tolerance. Additionally, its synthetic practicality is highlighted by gram-scalability and the late-stage modification of natural compounds. Mechanistic experiments suggest that this process involves in situ formation of an imine intermediate via base-promoted elimination of HF.
A new generation of terminal copper nitrenes and their application in aromatic C-H amination reactions
Amarouch, Benedikt,G?bgen, Kai C.,Hoffmann, Alexander,Oster, Matthias,Sch?n, Florian,Steden, Dominik,Thomas, Fabian
supporting information, p. 6444 - 6462 (2021/05/26)
Copper nitrene complexes are highly reactive species and are known as intermediates in the copper catalyzed C-H amination. In this study, three novel copper tosyl nitrene complexes were synthesized at low temperatures, stabilized with heteroscorpionate ligands of the bis(pyrazolyl)methane family. The copper nitrenes were obtained by the reaction of a copper(i) acetonitrile complex with SPhINTs in dichloromethane. We show that the ligand design has a major influence on the catalytic activity and the thermal stability of the copper nitrene complex. Not only the choice of the third N donor, but also the substituent in the 5-position of the pyrazolyl moiety, have an impact on the stability. Furthermore, the novel copper nitrene complexes were used for catalytic aziridination of styrenes and C-H amination reactions of aromatic and aliphatic substrates under mild reaction conditions. Even challenging substrates like benzene and cyclohexane were aminated with good yields. The copper nitrene complexes were characterized using UV/Vis spectroscopy, low temperature Evans NMR spectroscopy, density functional theory, domain-based local pair natural orbital coupled cluster calculations (DLPNO-CCSD(T)) and cryo-UHR mass spectrometry.
