Synthesis of Unsymmetrical Vicinal Diamines via Directed Hydroamination
Byung Joo Lee, Andrew R. Ickes, Anil K. Gupta, Seth C. Ensign, Tam D. Ho, Anika Tarasewicz, Evan P. Vanable, Gregory D. Kortman and Kami L. Hull*
*Department of Chemistry, University of Texas at Austin, 105 E 24th St., Austin, Texas 78712, United States,
Email: kamihull
utexas.edu
B. J. Lee, A. R. Ickes, A. K. Gupta, S. C. Ensign, T. D. Ho, A. Tarasewicz, E. P. Vanable, G. D. Kortman, K. L. Hull, Org. Lett., 2022, 24, 5513-5518.
DOI: 10.1021/acs.orglett.2c01911
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Abstract
A rhodium-catalyzed hydroamination of primary and secondary allylic amines using diverse amine nucleophiles, including primary, secondary, acyclic, and cyclic aliphatic amines provides a wide range of unsymmetrical vicinal diamines. This methodology enables a the rapid synthesis of several bioactive molecules and analogs.
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General Procedure
[(DPEphos)Rh(COD)]BF4 (3.3 mg, 0.004 mmol, 2.0 mol %), allylamine (0.20 mmol, 1.0 equiv), amine nucleophile (0.4 mmol, 2.0 equiv), and dry CH3CN (50 μL) are added to an oven-dried 4 mL vial equipped with a stir bar in the glove box. The resulting solution is allowed to stir for 24 h at the indicated temperature. The reaction vial is cooled to room temperature and is concentrated in vacuo followed by drying under high vacuum to afford the crude diamines as yellow oil. The crude residue is loaded to the column by transferring with dichloromethane (ca. 1 mL) and columned using the method described in detail in the supporting information.
Key Words
ID: J54-Y2022
