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.

Key words

aminations - enaminoketones - homogenous catalysis - propargyl alcohols - ruthenium

References and Notes

• 1a Shvo Y. Czarkie D. J. Am. Chem. Soc.  1986,  108:  7400 
• 1b Jung HM. Shin ST. Kim YH. Kim M.-J. Park J. Organometallics  2001,  20:  3370 
• 1c Jung HM. Choi JH. Lee SO. Kim YH. Park JH. Park J. Organometallics  2002,  21:  5674 
• 2 Menashe N. Shvo Y. Organometallics  1991,  10:  3885 
• 3 Shvo Y. Czarkie D. J. Organomet. Chem.  1986,  315:  C25 
• 4a Almeida MLS. Beller M. Wang G.-Z. Bäckvall J.-E. Chem. Eur. J.  1996,  2:  1533 
• 4b Almeida MLS. Kocovsky P. Bäckvall J.-E. J. Org. Chem.  1996,  61:  6587 
• 4c Csjernyik G. Ell AH. Fadini L. Pugin B. Bäckvall J.-E. J. Org. Chem.  2002,  67:  1657 
• 5 Ell AH. Samec JSM. Brasse C. Bäckvall J.-E. Chem. Commun.  2002,  1144 
• 6a Larsson ALE. Persson BA. Bäckvall J.-E. Angw. Chem., Int. Ed. Engl.  1997,  36:  1211 
• 6b Larsson ALE. Persson BA. Ray ML. Bäckvall J.-E. J. Am. Chem. Soc.  1999,  121:  1645 
• 6c Pamies O. Bäckvell J.-E. Chem. Rev.  2003,  103:  3247 
• 7 Pamies O. Ell AH. Samec JSM. Hermanns N. Bäckvell J.-E. Tetrahedron Lett.  2002,  43:  4699 
• 8 Choi JH. Kim N. Shin YJ. Park JH. Park J. Tetrahedron Lett.  2004,  45:  4607 
• 9a Blum Y. Shvo Y. Chodosh DF. Inorg. Chim. Acta  1985,  97:  C25 
• 9b Blum Y. Shvo Y. Czarkie D. Rahamim Y. Organometallics  1985,  4:  1459 
• 9c Blum Y. Shvo Y. Isr. J. Chem.  1984,  24:  144 

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.