Zirconium-Catalyzed Intermolecular Hydroamination of Unactivated Olefins

Abstract

Highly efficient hydroamination reactions of sulfon­amides, carboxamides, and carbamates with unactivated olefins catalyzed by simple and inexpensive zirconium salts under mild reaction conditions were presented for the practical preparation of various amines. These processes gave good to excellent yields of the addition products in Markovnikov addition fashion.

Key words

hydroamination - olefins - amides - carbamates - zirconium salts

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14

During the preparation of our manuscript, several related papers using other metal salts dealing with the intermolecular hydroamination of styrenes have appeared in the literature, see ref. 10a-c.

15

Typical Procedure for Intermolecular Addition Reactions of Olefins
Into a test tube were placed Zr(OTf)₄ (0.05 mmol) and NH₂Ts (1 mmol). After the test tube was sealed, it was purged three times with argon, then n-heptane (2 mL) and cyclohexene (2 mmol) were injected. The reaction mixture was heated at 85 ˚C and stirred vigorously for 20 h. After the reaction was completed, the mixture was directly applied to column chromatography using SiO₂ (EtOAc-PE, 1:10 to 1:5) to afford a analytically pure product (93% isolated yield). All the compounds are known and NMR or GC-MS data for some representative products are given below.
N -(1-Phenylethyl)benzamide ^¹H NMR (400 MHz, CDCl₃): δ = 7.77 (d, J = 7.2 Hz, 2 H), 7.50-7.46 (t, 1 H), 7.42-7.35 (m, 6 H), 7.33-7.25 (m, 1 H), 6.44 (br, 1 H), 5.34 (dt, J = 7.2, 7.2 Hz, 1 H), 1.60 (d, J = 6.8 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 166.56, 143.08, 134.51, 131.42, 128.70, 128.50, 127.40, 126.89, 126.21, 49.17, 21.68. GC-MS: m/z = 225.
N -[1-(4-Bromophenyl)ethyl]-4-methylbenzenesulfon-amide
^¹H NMR (400 MHz, CDCl₃): δ = 7.57 (d, J = 8.4 Hz, 2 H), 7.27 (d, J = 8.4 Hz, 2 H,), 7.16 (d, J = 8.0 Hz, 2 H), 6.97 (d, J = 8.0 Hz, 2 H), 5.42 (d, J = 7.2 Hz, 1 H), 4.41 (quint, J = 6.8 Hz, 1 H), 2.39 (s, 3 H), 1.37 (d, J = 6.8 Hz, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 143.32, 140.00, 137.33, 131.43, 129.42, 127.92, 127.00, 121.16, 53.06, 23.35, 21.47. GC-MS: m/z = 354. Cyclohex-2-enyl- p -toluenesulfonamide
^¹H NMR (400 MHz, CDCl₃): δ = 7.75 (d, J = 7.6 Hz, 2 H), 7.27 (d, J = 8.0 Hz, 2 H), 5.71 (d, J = 10.0 Hz, 1 H), 5.31 (d, J = 10.4 Hz, 1 H), 4.84 (d, J = 8.4 Hz, 1 H), 3.77 (s, 1 H), 2.39 (s, 3 H), 1.94-1.77 (m, 2 H), 1.74-1.61 (m,1 H), 1.57-1.50 (m, 3 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 143.14, 138.24, 131.39, 129.60, 126.95, 126.91, 48.89, 30.12, 24.38, 21.45, 19.22. GC-MS: m/z = 251.