Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in N-alkyl amides by an excited-state iridium photocatalyst and a dialkyl phosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. The feasibility of this PCET protocol in enabling the intermolecular anti-Markovnikov hydroamidation reactions of unactivated olefins is also demonstrated.
Olefin aminations are important synthetic technologies for the construction of aliphatic C-N bonds. Here we report a catalytic protocol for n class="Chemical">olefin hydroamidation that proceeds through transient amidyl radical intermediates that are formed via proton-coupled electron transfer (PCET) activation of the strong N-H bonds in N-alkyl amides by an excited-state iridium photocatalyst and a dialkylphosphate base. This method exhibits a broad substrate scope, high functional group tolerance, and amenability to use in cascade polycyclization reactions. The feasibility of this PCET protocol in enabling the intermolecular anti-Markovnikov hydroamidation reactions of unactivated olefins is also demonstrated.
Entities:
Keywords:
amidyl radicals; hydroamidation; hydrogen atom transfer; photoredox catalysis; proton-coupled electron transfer
Authors: Rebecca L Lalonde; William E Brenzovich; Diego Benitez; Ekaterina Tkatchouk; Kotaro Kelley; William A Goddard; F Dean Toste Journal: Chem Sci Date: 2010-08-01 Impact factor: 9.825
Authors: Jill B Williamson; William L Czaplyski; Erik J Alexanian; Frank A Leibfarth Journal: Angew Chem Int Ed Engl Date: 2018-04-23 Impact factor: 15.336
Authors: David C Miller; Jacob M Ganley; Andrew J Musacchio; Trevor C Sherwood; William R Ewing; Robert R Knowles Journal: J Am Chem Soc Date: 2019-10-14 Impact factor: 15.419
Authors: Katherine C Forbes; Anne Marie Crooke; Yuri Lee; Masamu Kawada; Kian M Shamskhou; Rachel A Zhang; Jeffrey S Cannon Journal: J Org Chem Date: 2022-02-08 Impact factor: 4.354
Authors: Philip R D Murray; James H Cox; Nicholas D Chiappini; Casey B Roos; Elizabeth A McLoughlin; Benjamin G Hejna; Suong T Nguyen; Hunter H Ripberger; Jacob M Ganley; Elaine Tsui; Nick Y Shin; Brian Koronkiewicz; Guanqi Qiu; Robert R Knowles Journal: Chem Rev Date: 2021-11-23 Impact factor: 60.622
Authors: Jessica G K O'Brien; Andrew Jemas; Papa Nii Asare-Okai; Christopher W Am Ende; Joseph M Fox Journal: Org Lett Date: 2020-12-01 Impact factor: 6.005
Authors: Yangzhong Qin; Qilei Zhu; Rui Sun; Jacob M Ganley; Robert R Knowles; Daniel G Nocera Journal: J Am Chem Soc Date: 2021-06-30 Impact factor: 16.383