Asymmetric Hydroamination
Manage episode 311760745 series 3180620
In this episode we discuss a report from the Hartwig lab on an enantioselective hydroamination reaction. Through rational catalyst design, a cationic iridium complex was discovered that adds an amine N–H bond across a range of unactivated, internal alkenes.
DOI: 10.1038/s41586-020-2919-z
Xi, Y.; Ma, S.; Hartwig, J. F. Catalytic asymmetric addition of an amine N–H bond across internal alkenes. Nature 2020.
Nguyen, T. M.; Manohar, N.; Nicewicz, D. A. anti-Markovnikov Hydroamination of Alkenes Catalyzed by a Two-Component Organic Photoredox System: Direct Access to Phenethylamine Derivatives. Angew. Chem. Int. Ed. 2014, 53, 6198–6201.
Musacchio, A. J.; Lainhart, B. C.; Zhang, X.; Naguib, S. G.; Sherwood, T. C.; Knowles, R. R. Catalytic intermolecular hydroaminations of unactivated olefins with secondary alkyl amines. Science, 2017, 355, 727–730.
Huang, L.; Arndt, M.; Gooßen, K.; Heydt, H.; Gooßen, L. J. Late Transition Metal-Catalyzed Hydroamination and Hydroamidation. Chem. Rev. 2015, 115, 2596–2697.
Gurak, J. A.; Yang, K. S.; Liu, Z.; Engle, K. M. Directed, Regiocontrolled Hydroamination of Unactivated via Protodepalladation. J. Am. Chem. Soc. 2016, 138, 5805–5808.
Vanable, E. P.; Kennemur, J. L.; Joyce, L. A.; Ruck, R. T.; Schultz, D. M.; Hull, K. L. Rhodium-Catalyzed Asymmetric Hydroamination of Allyl Amines. J. Am. Chem. Soc. 2019, 141, 739–742.
Zhang, J.; Yang, C.-G.; He, C. Gold(I)-Catalyzed Intra- and Intermolecular Hydroamination of Unactivated Olefins. J. Am. Chem. Soc. 2006, 128, 1798–1799.
Zhang, Z.; Lee, S. D.; Widenhoefer, R. A. Intermolecular Hydroamination of Ethylene and 1-Alkenes with Cyclic Ureas Catalyzed by Achiral and Chiral Gold(I) Complexes. J. Am. Chem. Soc. 2009, 131, 5372– 5373.
Zhou, J.; Hartwig, J. F. Intermolecular, Catalytic Asymmetric Hydroamination of Bicyclic Alkenes and Dienes in High Yield and Enantioselectivity. J. Am. Chem. Soc. 2008, 130, 12220–12221.
Sevov, C. S.; Zhou, J.; Hartwig, J. F. Iridium-Catalyzed Intermolecular Hydroamination of Unactivated Aliphatic Alkenes with Amides and Sulfonamides. J. Am. Chem. Soc. 2012, 134, 11960–11963.
Hanley, P. S.; Hartwig, J. F. Intermolecular Migratory Insertion of Unactivated Olefins into Palladium-Nitrogen Bonds. Steric and Electronic Effects on the Rate of Migratory Insertion. J. Am. Chem. Soc. 2011, 133, 15661–15673.
Pan, S.; Endo, K.; Shibata, T. Ir(I)-Catalyzed Intermolecular Regio- and Enantioselective Hydroamination of Alkenes with Heteroaromatic Amines. Org. Lett. 2012, 14, 780–783.
Casalnuovo, A. L.; Calabrese, J. C.; Milstein, D. Rational design in homogeneous catalysis. Iridium(I)-catalyzed addition of aniline to norbornylene via nitrogen-hydrogen activation. J. Am. Chem. Soc. 1988, 110, 6738–6744.
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