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10.1021/jacs.7b01446 http://scihub22266oqcxt.onion/10.1021/jacs.7b01446 C5374491!5374491!28281754     free     free     free Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534 Deprecated: Implicit conversion from float 213.6 to int loses precision in C:\Inetpub\vhosts\kidney.de\httpdocs\pget.php on line 534       J+Am+Chem+Soc 2017 ; 139 (12): 4559-67 Nephropedia Template TP {{tp|p=28281754|t=2017. Studies on the Enantioselective Iminium Ion Trapping of Radicals Triggered by an Electron-Relay Mechanism |pdf=|usr=}}{{28281754}} gab.com Text Studies on the Enantioselective Iminium Ion Trapping of Radicals Triggered by an Electron-Relay Mechanism JO: J Am Chem Soc http://www.kidney.de/pget.php?&tw=1&pmid=28281754 #FOAvip A combination of electrochemical, spectroscopic, computational, and kinetic studies has been used to elucidate the key mechanistic aspects of the previously reported enantioselective iminium ion trapping of photochemically generated carbon-centered radicals. The process, which provides a direct way to forge quaternary stereocenters with high fidelity, relies on the interplay of two distinct catalytic cycles: the aminocatalytic electron-relay system, which triggers the stereoselective radical trap upon iminium ion formation, and the photoredox cycle, which generates radicals under mild conditions. Critical to reaction development was the use of a chiral amine catalyst, bearing a redox-active carbazole unit, which could rapidly reduce the highly reactive and unstable intermediate generated upon radical interception. The carbazole unit, however, is also involved in another step of the electron-relay mechanism: the transiently generated carbazole radical cation acts as an oxidant to return the photocatalyst into the original state. By means of kinetic and spectroscopic studies, we have identified the last redox event as being the turnover-limiting step of the overall process. This mechanistic framework is corroborated by the linear correlation between the reaction rate and the reduction potential of the carbazole unit tethered to the aminocatalyst. The redox properties of the carbazole unit can thus be rationally tuned to improve catalytic activity. This knowledge may open a path for the mechanistically driven design of the next generation of electron-relay catalysts. Twit Text FOAVip Studies on the Enantioselective Iminium Ion Trapping of Radicals Triggered by an Electron-Relay Mechanism ????J Am Chem Soc http://www.kidney.de/pget.php?&tw=1&pmid=28281754 #FOAvip Twit Text # Free Paper on # # # # # LINK http://www.kidney.de/pget.php?&tw=1&pmid=28281754 #FOAvip English Wikipedia <ref>{{Cite pmid|28281754}}</ref> Studies on the Enantioselective Iminium Ion Trapping of Radicals Triggered by an Electron-Relay Mechanism #MMPMID28281754 Bahamonde A; Murphy JJ; Savarese M; Brémond É; Cavalli A; Melchiorre P J Am Chem Soc 2017[Mar]; 139 (12): 4559-67 PMID28281754show ga A combination of electrochemical, spectroscopic, computational, and kinetic studies has been used to elucidate the key mechanistic aspects of the previously reported enantioselective iminium ion trapping of photochemically generated carbon-centered radicals. The process, which provides a direct way to forge quaternary stereocenters with high fidelity, relies on the interplay of two distinct catalytic cycles: the aminocatalytic electron-relay system, which triggers the stereoselective radical trap upon iminium ion formation, and the photoredox cycle, which generates radicals under mild conditions. Critical to reaction development was the use of a chiral amine catalyst, bearing a redox-active carbazole unit, which could rapidly reduce the highly reactive and unstable intermediate generated upon radical interception. The carbazole unit, however, is also involved in another step of the electron-relay mechanism: the transiently generated carbazole radical cation acts as an oxidant to return the photocatalyst into the original state. By means of kinetic and spectroscopic studies, we have identified the last redox event as being the turnover-limiting step of the overall process. This mechanistic framework is corroborated by the linear correlation between the reaction rate and the reduction potential of the carbazole unit tethered to the aminocatalyst. The redox properties of the carbazole unit can thus be rationally tuned to improve catalytic activity. This knowledge may open a path for the mechanistically driven design of the next generation of electron-relay catalysts. äStudies on the Enantioselective Iminium Ion Trapping of Radicals Trigg(epmc).pdf DeepDyve Pubget Overpricing