Ruthenium-Catalyzed Enaminoketone Formation from Propargyl Alcohols

Abstract

Monomeric ruthenium(0) complexes containing electronically coupled dienone ligands were found to catalyze the ­formation of enaminoketones from propargyl alcohols.

aminations - enaminoketones - homogenous catalysis - propargyl alcohols - ruthenium

References and Notes

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10

Characterization Data for Typical Enaminoketones.
Compound E-7c: C₁₅H₁₇NO₃, yellow oil (rotamers 4:1). ¹H NMR (300 MHz, CDCl₃): δ = 1.90-2.34 (m, 4 H), 3.50-3.55 (m, 2 H), 3.75 (s, 3 H), 4.16 and 4.29 (t, J = 8.1 Hz, 1 H), 5.67 and 5.77 (d, J = 12.4 Hz, 1 H), 7.37-7.46 (m, 3 H), 7.87-8.01 (m, 3 H). ¹³C NMR (75 MHz, DEPT, CDCl₃): δ = 23.2 and 25.1 (CH₂), 27.5 and 29.7 (CH₂), 45.1 and 46.0 (CH₂), 52.5 (CH₃), 60.4 and 60.9 (CH), 92.9 and 94.8 (CH), 127.4 and 127.5 (CH), 127.9 and 128.0 (CH), 130.6 and 131.0 (CH), 140.0 and 140.5 (C), 149.3 and 149.8 (CH), 166.3 and 172.1, 188.8 (C). IR: 3056, 3024, 2956, 2878, 1741, 1662, 1633, 1580, 1539, 1449, 1364, 1340, 1304, 1274, 1209, 1166, 1090, 1051, 1026, 1008, 991, 925, 893, 837, 758, 706, 621, 557 cm^-1. MS (EI): m/z (%) = 259 (45) [M⁺], 200 (100), 172 (34), 154 (58), 105 (70), 77 (54), 70 (36). HRMS: m/z calcd: 259.12085; found: 259.12007.
Compound Z-7d: C₁₂H₁₃NO, yellow oil. ¹H NMR (400 MHz, CDCl₃): δ = 3.89 (tt, J = 5.6, 1.6 Hz, 2 H), 5.21 (dq, J = 10.2, 1.4 Hz, 1 H), 5.27 (dq, J = 17.1, 1.7 Hz, 1 H), 5.75 (d, J = 7.5 Hz, 1 H), 5.90 (ddt, J = 17.1, 10.3, 5.1 Hz, 1 H), 6.93 (dd, J = 12.8, 7.5 Hz, 1 H), 7.38-7.44 (m, 3 H), 7.88 (dd, J = 8.2, 1.4 Hz, 2 H), 10.3 (br s, NH). ¹³C NMR (100 MHz, DEPT, CDCl₃): δ = 51.0 (CH₂), 90.7 (CH), 117.1 (CH₂), 127.0 (CH), 128.2 (CH), 130.9 (CH), 134.2 (CH), 139.7 (C), 154.0 (CH), 190.1 (C). IR: 3271, 3059, 3027, 2921, 2855, 1627, 1582, 1541, 1499, 1476, 1442, 1363, 1272, 1227, 1205, 1161, 1048, 1021, 988, 922, 867, 734, 699, 554 cm^-1. MS (EI): m/z (%) = 187(58) [M⁺], 186 (39), 105 (100), 82 (89), 77 (55). HRMS: m/z calcd: 187.09972; found: 187.09941.