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DOI: 10.1055/s-2007-967986
Allenic Pauson-Khand Reaction Catalyzed by Cobalt-Rhodium Heterobimetallic Nanoparticles
Ji Hoon Park, Sun Young Kim, Soo Min Kim, Sang Ick Lee, Young Keun Chung*Intelligent Textile System Research Center and Department of Chemistry, College of Natural Sciences, Seoul National University, Seoul 151-747, Korea
Fax: +82(2)8890310; e-Mail: ykchung@snu.ac.kr;
Publication History
Received
8 November 2006
Publication Date:
07 February 2007 (online)
Abstract
Pauson-Khand reaction of allenynes, catalyzed by Co-Rh heterobimetallic nanoparticles, was developed for the synthesis of [5.6]- and [5.7]-bicyclic enones. The cyclization occurred selectively with the distal double bond of the allene. The catalytic system could be used at least six times without loss of catalytic activity.
Key words
allenes - alkynes - carbonylations - Pauson-Khand reaction - nanoparticle
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References and Notes
To a two-neck flask were added o-dichlorobenzene (24 mL), oleic acid (0.2 mL), and trioctylphosphine oxide (0.4 g). While the solution was heated at 180 °C, a solution of metal carbonyl, Co2Rh2(CO)12 (1.0 g) in 6 mL of o-dichloro-benzene was injected into the flask. The resulting solution was heated at 180 °C for 2 h. After the solution was cooled, the solution was concentrated to a volume of ca. 10 mL by distillation. To the concentrated solution were added 200 mL of THF and then flame-dried charcoal (2.0 g). The resulting THF solution was refluxed with stirring for 18 h and then cooled to r.t. under nitrogen atmosphere. After the solution was filtered, the precipitate was washed successively with Et2O, CH2Cl2, acetone, and MeOH and dried in vacuo.
16
Analytical Data.
Compound 1A: IR: 1702 cm-1. 1H NMR (300 MHz): δ = 1.78 (s, 3 H), 2.40 (s, 3 H), 2.76 (s, 2 H), 3.94 (d, 2 H, J = 3.7 Hz), 4.25 (s, 2 H), 5.74 (t, 1 H, J = 3.7 Hz), 7.30 (d, 2 H, J = 8.0 Hz), 7.67 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 7.9, 21.4, 37.2, 43.3, 44.6, 117.6, 127.6, 129.7, 133.6, 133.8, 136.0, 144.1, 155.9, 203.7 ppm. HRMS (EI): m/z calcd for C16H17NO3S: 303.0929; found: 303.0926.
Compound 2A: IR: 1704 cm-1. 1H NMR (300 MHz): δ = 2.42 (s, 3 H), 2.80 (s, 2 H), 3.95 (d, 2 H, J = 3.6 Hz), 4.31 (s, 2 H), 5.56 (t, 1 H, J = 3.6 Hz), 5.97 (s, 1 H), 7.31 (d, 2 H, J = 8.1 Hz), 7.67 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 21.5, 37.7, 44.3, 44.5, 120.5, 127.5, 127.7, 129.8, 133.6, 135.0, 144.1, 162.2, 203.5 ppm. HRMS (EI): m/z calcd for C15H15NO3S: 289.0773; found: 289.0775.
Compound 3A: IR: 1702 cm-1. 1H NMR (300 MHz): δ = 2.42 (s, 3 H), 2.89 (s, 2 H), 4.06 (d, 2 H, J = 3.5 Hz), 4.49 (s, 2 H), 5.88 (t, 1 H, J = 3.5 Hz), 7.27 (m, 2 H), 7.33 (d, 2 H, J = 8.1 Hz), 7.44 (m, 3 H), 7.59 (d, 2 H, J = 8.1 Hz) ppm. 13C NMR (75 MHz): δ = 21.7, 38.2, 44.3, 45.1, 120.1, 127.8, 128.9, 129.0, 129.9, 130.1, 134.06, 134.09, 138.0, 156.0, 202.0 ppm. HRMS (EI): m/z calcd for C21H19NO3S: 365.1086; found: 365.1086.
Compound 4a: IR: 1910 cm-1. 1H NMR (300 MHz): δ = 0.82 (t, 3 H, J = 7.4 Hz), 1.84 (q, 2 H, J = 7.3 Hz), 2.33 (s, 3 H), 3.77 (m, 2 H), 4.03 (s, 2 H), 4.69 (m, 2 H), 4.97 (m, 1 H), 7.21 (d, 2 H, J = 7.8 Hz), 7.65 (d, 2 H, J = 8.0 Hz) ppm. 13C NMR (75 MHz): δ = 12.2, 13.6, 21.6, 36.5, 45.6, 71.6, 76.4, 85.7, 87.6, 127.8, 129.4, 136.2, 143.4, 209.8 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1137.
Compound 4A: IR: 1701 cm-1. 1H NMR (300 MHz): δ = 1.04 (t, 3 H, J = 7.6 Hz), 2.26 (q, 2 H, J = 7.5 Hz), 2.42 (s, 3 H), 2.76 (s, 2 H), 3.95 (d, 2 H, J = 3.2 Hz), 4.28 (s, 2 H), 5.75 (t, 1 H, J = 3.1 Hz), 7.30 (d, 2 H, J = 8.0 Hz), 7.67 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 12.7, 16.5, 21.7, 37.6, 43.3, 44.7, 118.0, 127.8, 129.9, 133.7, 134.0, 141.6, 144.2, 155.6, 203.7 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1087.
Compound 5a: IR: 1736, 1952 cm-1. 1H NMR (300 MHz): δ = 1.75 (s, 3 H), 2.76 (m, 2 H), 2.79 (s, 2 H), 3.73 (s, 6 H), 4.67 (m, 2 H) 4.93 (m, 1 H) ppm. 13C NMR (75 MHz): δ = 3.7, 23.2, 31.9, 52.9, 57.7, 73.3, 74.8, 79.2, 84.1, 170.6, 210.3 ppm. FAB-HRMS: m/z calcd for C13H17O4: 237.1127; found: 237.1130.
Compound 5A: IR: 1696, 1736 cm-1. 1H NMR (300 MHz): δ = 1.80 (s, 3 H), 2.85-2.87 (m, 4 H), 3.12 (s, 2 H), 3.71 (s, 6 H), 5.76 (m, 1 H) ppm. 13C NMR (75 MHz): δ = 8.0, 30.4, 31.2, 37.9, 53.3, 54.3, 119.1, 135.3, 137.4, 160.0, 170.9, 205.1 ppm. HRMS (EI): m/z calcd for C14H16O5: 264.0998; found: 264.1003.
Compound 6a: IR: 1946, 1734 cm-1. 1H NMR (300 MHz): δ = 2.84 (td, 2 H, J = 2.3, 8.0 Hz), 3.08 (s, 2 H), 3.76 (s, 6 H), 4.70 (td, 2 H, J = 2.3, 6.5 Hz), 5.01 (m, 1 H), 7.27 (m, 3 H), 7.37 (dd, 2 H, J = 3.1, 6.6 Hz) ppm. 13C NMR (75 MHz): δ = 23.9, 32.1, 52.6, 53.0, 57.7, 75.0, 83.8, 84.0, 84.3, 123.4, 128.2, 128.39, 128.43, 128.9, 131.8, 170.4 ppm. HRMS (EI): m/z calcd for C18H18O4: 298.1205; found: 298.1205.
Compound 6A: IR: 1736, 1694 cm-1. 1H NMR (300 MHz): δ = 2.97 (d, 2 H, J = 4.3 Hz), 3.07 (s, 2 H), 3.34 (s, 2 H), 3.73 (s, 6 H), 5.97 (t, 1 H, J = 4.3 Hz), 7.39 (m, 5 H) ppm. 13C NMR (75 MHz): δ = 30.4, 31.3, 31.5, 38.7, 76.5, 121.7, 128.4, 128.6, 129.2, 131.0, 135.1, 139.3, 160.1, 170.9, 203.1 ppm. HRMS (EI): m/z calcd for C19H18O5: 326.1154; found: 326.1154.
Compound 7a: IR: 1944 cm-1. 1H NMR (300 MHz): δ = 1.86 (t, 3 H, J = 2.2 Hz), 4.07 (td, 2 H, J = 2.3, 6.8 Hz), 4.12 (d, 2 H, J = 2.3 Hz), 4.80 (td, 2 H, J = 2.3, 6.3 Hz), 5.23 (m, 1 H, J = 6.8 Hz) ppm. 13C NMR (75 MHz): δ = 3.6, 57.5, 67.3, 74.9, 75.8, 82.6, 87.3, 209.5 ppm. HRMS (EI): m/z calcd for C8H10O: 122.0732; found: 122.0729.
Compound 7A: IR: 1698 cm-1. 1H NMR (300 MHz): δ = 1.77 (s, 3 H), 2.95 (s, 2 H), 4.32 (d, 2 H, J = 3.1 Hz), 4.67 (s, 2 H), 5.95 (s, 1 H, J = 3.3 Hz) ppm. 13C NMR (75 MHz): δ = 8.0, 37.5, 63.8, 65.0, 121.4, 132.9, 133.6, 158.8, 204.6 ppm. HRMS (EI): m/z calcd for C9H10O2: 150.0681; found: 150.0680.
Compound 8a: IR: 1950 cm-1. 1H NMR (300 MHz): δ = 4.17 (d, 2 H, J = 6.7 Hz), 4.40 (s, 2 H), 4.83 (m, 2 H), 5.28 (t, 1 H, J = 6.7 Hz), 7.29 (m, 3 H), 7.47 (m, 2 H) ppm. 13C NMR (75 MHz): δ = 57.8, 67.6, 76.1, 85.0, 86.5, 87.4. 122.8, 128.5, 128.6, 132.0, 209.8 ppm. HRMS (EI): m/z calcd for C13H12O: 184.0888; found: 184.0890.
Compound 8A: IR: 1696 cm-1. 1H NMR (300 MHz): δ = 3.14 (s, 2 H), 4.39 (d, 2 H, J = 1.5 Hz), 4.87 (s, 2 H), 6.14 (t, 1 H, J = 1.5 Hz), 7.40 (m, 5 H) ppm. 13C NMR (75 MHz): δ = 38.4, 64.5, 65.1, 123.8, 128.6, 128.7, 128.9, 130.6, 132.8, 135.4, 159.1, 202.5 ppm. HRMS (EI): m/z calcd for C14H12O2): 212.0837; found: 212.0840.
Compound 9a: IR: 1944 cm-1. 1H NMR (300 MHz): δ = 0.00 (m, 9 H), 2.42 (s, 3 H), 3.87 (m, 2 H), 4.17 (s, 2 H), 4.79 (m, 2 H), 5.06 (m, 1 H), 7.30 (d, 2 H, J = 8.0 Hz), 7.74 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 0.0, 21.8, 37.2, 45.9, 85.7, 91.3, 97.9, 128.1, 129.8, 136.3, 143.7, 210.2 ppm. HRMS (EI): m/z calcd for C17H23NO2SSi: 333.1219; found: 333.1215.
Compound 9A: IR: 1696 cm-1. 1H NMR (300 MHz): δ = 0.26 (s, 9 H), 2.41 (s, 3 H), 2.71 (s, 2 H), 3.96 (d, 2 H, J = 3.2 Hz), 4.36 (s, 2 H), 5.81 (t, 1 H, J = 3.2 Hz), 7.28 (d, 2 H, J = 8.0 Hz), 7.64 (d, 2 H, J = 8.1 Hz) ppm. 13C NMR (75 MHz): δ = -0.7, 21.6, 38.5, 44.5, 45.4, 119.4, 127.7, 129.8, 134.0, 136.5, 140.2, 144.2, 168.0, 208.0 ppm. HRMS (EI): m/z calcd for C18H23NO3SSi: 361.1168; found: 361.1169.
Compound 10a: IR: 1952 cm-1. 1H NMR (300 MHz): δ = 1.24 (d, 3 H, J = 6.9 Hz), 1.67 (t, 3 H, J = 2.2 Hz), 2.41 (s, 3 H), 3.90 (dd, 1 H, J = 2.3, 4.5 Hz), 4.08 (dd, 1 H, J = 2.3, 4.5 Hz), 4.61 (m, 1 H), 4.78 (d, 1 H, J = 3.5 Hz), 4.80 (d, 1 H, J = 3.5 Hz), 5.07 (dd, 1 H, J = 6.5, 11.9 Hz), 7.28 (d, 2 H, J = 8.1 Hz), 7.79 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 3.4, 18.0, 21.5, 32.6, 51.8, 75.3, 77.7, 80.1, 91.8, 127.5, 129.3, 138.0, 143.1, 208.6 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1136.
Compound 10A: IR: 1701 cm-1. 1H NMR (300 MHz): δ = 1.34 (d, 3 H, J = 6.8 Hz), 1.75 (s, 3 H), 2.35 (s, 3 H), 2.43 (d, 1 H, J = 20.8 Hz), 2.72 (d, 1 H, J = 20.9 Hz), 4.15 (d, 1 H, J = 18.5 Hz), 4.70 (m, 1 H), 4.89 (d, 1 H, J = 18.5 Hz), 5.64 (d, 1 H, J = 5.0 Hz), 7.17 (d, 2 H, J = 8.0 Hz), 7.57 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 8.0, 19.5, 12.6, 37.3, 39.2, 50.3, 123.7, 127.3, 129.5, 132.7, 135.9, 136.5, 143.8, 155.2, 203.7 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1082.
Compound 11a: IR: 1946 cm-1. 1H NMR (300 MHz): δ = 1.41 (dd, 4 H, J = 8.1, 17.0 Hz), 1.60 (t, 4 H, J = 8.0 Hz), 1.70 (m, 2 H), 1.84 (t, 3 H, J = 2.3 Hz), 4.01 (dd, 2 H, J = 2.2, 4.5 Hz), 4.82 (d, 2 H, J = 6.7 Hz), 5.04 (t, 1 H, J = 6.7 Hz) ppm. 13C NMR (75 MHz): δ = 3.9, 22.4, 25.8, 35.2, 50.7, 76.4, 76.5, 77.0, 81.2, 95.3, 208.7 ppm. HRMS (EI): m/z calcd for C13H18O: 190.1358; found: 190.1360.
Compound 11A: IR: 1694 cm-1. 1H NMR (300 MHz): δ = 1.26-1.80 (m, 10 H), 1.76 (s, 3 H), 2.92 (s, 2 H), 4.70 (s, 2 H), 5.85 (s, 1 H) ppm. 13C NMR (75 MHz): δ = 8.0, 21.7, 25.5, 34.9, 37.7, 58.4, 73.3, 129.7, 131.3, 133.3, 159.1, 204.7 ppm. HRMS (EI): m/z calcd for C14H18O2: 218.1307; found: 218.1308.
Compound 12a: IR: 1957 cm-1. 1H NMR (300 MHz): δ = 1.50 (t, 3 H, J = 2.3 Hz), 1.71 (t, 3 H, J = 3.1 Hz), 2.42 (s, 3 H), 3.75 (t, 2 H, J = 2.2 Hz), 4.03 (dd, 2 H, J = 2.3, 4.6 Hz), 4.66 (dd, 2 H, J = 2.7, 5.5 Hz), 7.29 (d, 2 H, J = 8.1 Hz), 7.73 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 3.3, 16.0, 21.6, 36.3, 50.0, 71.5, 75.2, 81.6, 93.7, 128.0, 129.3, 136.4, 143.3, 207.7 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1138.
Compound 12A: IR: 1698 cm-1. 1H NMR (300 MHz): δ = 1.75 (s, 3 H), 1.76 (s, 3 H), 2.41 (s, 3 H), 2.68 (s, 2 H), 3.80 (s, 2 H), 4.20 (s, 2 H), 7.30 (d, 2 H, J = 8.0 Hz), 7.65 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 8.1, 18.0, 21.6, 16.1, 43.2, 18.7, 127.1, 127.6, 128.9, 129.8, 133.5, 134.3, 144.2, 156.7, 203.9 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1082.
Compound 13a: IR: 1932 cm-1. 1H NMR (300 MHz): δ = 1.48 (t, 3 H, J = 2.3 Hz), 2.43 (s, 3 H), 4.00 (q, 2 H, J = 2.3 Hz), 4.26 (t, 2 H, J = 2.2 Hz), 5.11 (t, 2 H, J = 2.1 Hz), 7.22 (t, 1 H, J = 7.3 Hz), 7.33 (m, 4 H), 7.54 (d, 2 H, J = 8.3 Hz), 7.77 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 3.3, 21.6, 36.3, 46.9, 71.2, 78.8, 82.0, 99.9, 126.5, 127.3, 128.2, 128.6, 129.3, 133.4, 135.7, 143.5, 210.1 ppm. HRMS (EI): m/z calcd for C21H21NO2S: 351.1293; found: 351.1290.
Compound 13A: IR: 1700 cm-1. 1H NMR (300 MHz): δ = 1.71 (s, 3 H), 2.28 (s, 3 H), 2.71 (s, 2 H), 4.16 (s, 2 H), 4.24 (s, 2 H), 7.14 (dd, 4 H, J = 7.6, 13.1 Hz), 7.26 (m, 3 H), 7.57 (d, 2 H, J = 8.1 Hz) ppm. 13C NMR (75 MHz): δ = 8.1, 21.5, 37.4, 43.4, 48.2, 127.2, 127.6, 128.4, 128.7, 129.3, 129.7, 130.5, 133.7, 135.3, 137.2, 144.2, 156.7, 203.9 ppm. HRMS (EI): m/z calcd for C22H21NO3S: 379.1242; found: 379.1242.
Compound 14a: IR: 1958 cm-1. 1H NMR (300 MHz): δ = 1.55 (t, 3 H, J = 2.4 Hz), 1.64 (dd, 3 H, J = 3.1, 7.1 Hz), 2.42 (s, 3 H), 3.80 (m, 2 H), 4.08 (m, 2 H), 4.95 (m, 1 H), 5.15 (m, 1 H), 7.29 (d, 2 H, J = 7.8 Hz), 7.73 (m, 2 H) ppm. 13C NMR (75 MHz): δ = 3.4, 14.1, 21.6, 36.4, 46.2, 71.7, 81.5, 85.6, 87.4, 127.9, 129.4, 136.3, 143.3, 206.5 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1133.
Compound 14A: IR: 1702 cm-1. 1H NMR (300 MHz): δ = 1.03 (d, 3 H, J = 7.5 Hz), 1.79 (s, 3 H), 2.40 (s, 3 H), 3.98 (s, 2 H), 4.28 (q, 2 H, J = 16.8 Hz), 5.68 (t, 1 H, J = 3.5 Hz), 7.28 (d, 2 H, J = 7.9 Hz), 7.66 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 8.1, 13.9, 21.6, 41.5, 43.4, 44.8, 116.6, 127.7, 129.8, 134.0, 134.4, 140.4, 144.2, 154.6, 207.1 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1086.
Compound 14B: IR: 1681 cm-1. 1H NMR (300 MHz): δ = 1.71 (s, 3 H), 2.19 (d, 3 H, J = 7.3 Hz), 2.44 (s, 3 H), 2.53 (dd, 1 H, J = 9.1, 10.7 Hz), 3.46 (t, 1 H, J = 8.9 Hz), 3.96 (m, 2 H), 4.25 (d, 1 H, J = 15.6 Hz), 6.08 (qd, 1 H, J = 7.3, 1.0 Hz), 7.34 (d, 2 H, J = 8.3 Hz), 7.73 (d, 2 H, J = 8.1 Hz) ppm. 13C NMR (75 MHz): δ = 9.3, 13.9, 21.8, 46.4, 46.8, 51.3, 127.6, 130.2, 133.7, 135.1, 136.0, 137.1, 144.2, 164.1, 197.0 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1086.
Compound 14C: 1H NMR (300 MHz): δ = 1.67 (d, 3 H, J = 6.8 Hz), 2.33 (s, 3 H), 3.73 (m, 2 H), 3.81 (s, 2 H), 4.96 (dd, 1 H, J = 1.7, 10.7 Hz), 5.13 (dd, 1 H, J = 1.7, 17.1 Hz), 5.51 (m, 2 H), 6.18 (dd, 1 H, J = 10.7, 17.1 Hz), 7.20 (d, 2 H, J = 8.0 Hz), 7.59 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 13.3, 21.6, 43.8, 45.5, 116.5, 118.9, 122.4, 127.8, 129.6, 133.8, 134.7, 136.8, 143.6 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1133.
Compound 15B: IR: 1684 cm-1. 1H NMR (300 MHz): δ = 1.69 (s, 3 H), 1.88 (s, 3 H), 2.26 (s, 3 H), 2.44 (s, 3 H), 2.52 (dd, 1 H, J = 9.2, 10.8 Hz), 3.48 (t, 1 H, J = 8.8 Hz), 3.93 (d, 1 H, J = 15.1 Hz), 4.10 (t, 1 H, J = 8.5 Hz), 4.23 (d, 1 H, J = 15.2 Hz), 7.34 (d, 2 H, J = 8.0 Hz), 7.73 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 9.4, 19.8, 21.7, 24.9, 46.0, 46.3, 51.5, 127.5, 130.1, 130.2, 133.9, 137.0, 144.2, 148.5, 161.6, 196.2 ppm. HRMS (EI): m/z calcd for C18H21NO3S: 331.1242; found: 331.1239.
Compound 15C: 1H NMR (300 MHz): δ = 1.70 (d, 3 H, J = 0.7 Hz), 1.75 (d, 3 H, J = 7.2 Hz), 2.41 (s, 3 H), 3.81 (d, 2 H, J = 3.4 Hz), 3.93 (s, 2 H), 4.61 (m, 1 H), 4.90 (dd, 1 H, J = 1.3, 2.3 Hz), 5.36 (t, 1 H, J = 3.6 Hz), 5.49 (dd, 1 H, J = 7.1, 14.3 Hz), 7.28 (d, 2 H, J = 7.9 Hz), 7.67 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 13.4, 21.6, 23.1, 44.0, 45.3, 115.1, 118.1, 123.7, 127.9, 128.5, 129.6, 134.2, 142.0, 143.6, 143.9 ppm. HRMS (EI): m/z calcd for C17H21NO2S: 303.1293; found: 303.1290.
Compound 16a: IR: 1956 cm-1. 1H NMR (300 MHz): δ = 1.47 (s, 10 H), 2.01 (s, 3 H), 2.34 (s, 3 H), 3.69 (d, 2 H, J = 6.8 Hz), 4.01 (s, 2 H), 4.76 (s, 1 H), 7.21 (d, 2 H, J = 7.6 Hz), 7.65 (d, 2 H, J = 7.7 Hz) ppm. 13C NMR (75 MHz): δ = 3.4, 21.6, 26.1, 27.3, 31.4, 36.1, 46.8, 71.7, 81.3, 83.7, 104.1, 127.9, 129.3, 136.4, 143.3, 200.7 ppm. HRMS (EI): m/z calcd for C20H25NO2S: 343.1606; found: 343.1603.
Compound 16C: 1H NMR (300 MHz): δ = 1.56 (m, 4 H), 1.73 (d, 3 H, J = 7.1 Hz), 1.85 (d, 2 H, J = 1.3 Hz), 2.01 (d, 2 H, J = 1.5 Hz), 2.41 (s, 3 H), 3.78 (d, 2 H, J = 3.3 Hz), 3.90 (s, 2 H), 5.28 (s, 1 H), 5.30 (s, 1 H), 5.45 (q, 1 H, J = 7.1 Hz), 7.28 (d, 2 H, J = 7.8 Hz), 7.67 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 13.4, 21.7, 22.3, 23.1, 25.4, 29.1, 44.1, 45.4, 117.9, 123.2, 126.1, 127.9, 129.1, 129.6, 134.2, 137.0, 142.4, 143.6 ppm. HRMS (EI): m/z calcd for C20H25NO2S: 343.1606; found: 343.1603.
Compound 17a: IR: 1952 cm-1. 1H NMR (300 MHz): δ = 1.56 (t, 3 H, J = 2.2 Hz), 2.28 (m, 2 H), 2.42 (s, 3 H), 3.24 (m, 2 H), 4.07 (d, 2 H, J = 2.2 Hz), 4.70 (m, 2 H), 5.08 (m, 1 H), 7.29 (d, 2 H, J = 8.2 Hz), 7.73 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 3.4, 21.7, 27.2, 37.2, 46.0, 72.0, 75.6, 81.7, 86.7, 128.0, 129.4, 136.3, 143.4, 209.1 ppm. HRMS (EI): m/z calcd for C15H19NO2S: 277.1137; found: 277.1135.
Compound 17A: IR: 1694 cm-1. 1H NMR (300 MHz): δ = 1.81 (s, 3 H), 2.42 (s, 3 H), 2.60 (dd, 2 H, J = 5.0, 10.4 Hz), 2.91 (s, 2 H), 3.53 (t, 2 H, J = 5.7 Hz), 4.40 (s, 2 H), 5.69 (t, 1 H, J = 4.7 Hz), 7.29 (d, 2 H, J = 8.1 Hz), 7.68 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 8.6, 21.7, 31.7, 41.6, 49.1, 49.3, 124.8, 127.2, 129.9, 134.6, 136.3, 140.5, 143.9, 161.1, 204.2 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1084.
Compound 18a: IR: 1952 cm-1. 1H NMR (300 MHz): δ = 2.05 (t, 1 H, J = 2.5 Hz), 2.30 (m, 2 H), 2.42 (s, 3 H), 3.29 (t, 3 H, J = 7.2 Hz), 4.14 (d, 2 H, J = 2.4 Hz), 4.70 (td, 2 H, J = 3.0, 6.4 Hz), 5.08 (m, 1 H), 7.29 (d, 2 H, J = 8.1 Hz), 7.72 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 21.7, 27.0, 36.6, 46.0, 74.0, 75.7, 76.7, 86.5, 127.8, 129.6, 136.0, 143.7, 209.0 ppm. HRMS (EI): m/z calcd for C15H17NO2S: 275.0980; found: 275.0974.
Compound 18A: IR: 1681 cm-1. 1H NMR (300 MHz): δ = 2.42 (s, 3 H), 2.63 (dd, 2 H, J = 5.2, 10.6 Hz), 2.97 (s, 2 H), 3.53 (t, 2 H, J = 5.7 Hz), 4.46 (s, 2 H), 5.82 (t, 1 H, J = 4.5 Hz), 6.13 (s, 1 H), 7.30 (d, 2 H, J = 8.1 Hz), 7.68 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 21.7, 31.9, 42.7, 49.2, 50.5, 127.3, 127.8, 130.0, 132.5, 135.5, 136.2, 144.0, 168.2, 204.3 ppm. HRMS (EI): m/z calcd for C16H17NO3S: 303.0929; found: 303.0933.
Compound 19a: IR: 1947 cm-1. 1H NMR (300 MHz): δ = 2.35 (m, 5 H), 3.33 (t, 2 H, J = 7.5 Hz), 4.36 (s, 2 H), 4.71 (td, 2 H, J = 3.0, 6.4 Hz), 5.12 (p, 1 H, J = 6.8 Hz), 7.07 (dd, 2 H, J = 1.6, 7.9 Hz), 7.24 (m, 5 H), 7.77 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 21.6, 27.2, 37.5, 46.2, 75.7, 81.9, 85.8, 86.6, 122.3, 127.9, 128.3, 126.6, 129.7, 131.7, 136.1, 143.6, 209.1 ppm. HRMS (EI): m/z calcd for C20H21NO2S: 351.1293; found: 351.1299.
Compound 19A: IR: 1702 cm-1. 1H NMR (300 MHz): δ = 2.39 (s, 3 H), 2.64 (dd, 2 H, J = 5.6, 11.3 Hz), 2.99 (s, 2 H), 3.59 (s, 1 H), 3.59 (t, 2 H, J = 5.9 Hz), 4.51 (s, 2 H), 5.80 (t, 1 H, J = 5.2 Hz), 7.22 (d, 2 H, J = 8.0 Hz), 7.29 (m, 2 H), 7.43 (m, 3 H), 7.53 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 21.6, 30.9, 42.0, 49.0, 49.1, 126.7, 127.1, 128.6, 128.8, 129.3, 129.7, 130.4, 134.7, 136.3, 142.8, 143.7, 161.6, 202.5 ppm. HRMS (EI): m/z calcd for C22H21NO3S: 379.1242; found: 379.1238.
Compound 20a: IR: 1954 cm-1. 1H NMR (300 MHz): δ = 2.35 (m, 2 H), 3.66 (t, 2 H, J = 6.7 Hz), 4.38 (s, 2 H), 4.70 (m, 2 H), 5.16 (m, 1 H), 7.31 (m, 3 H), 7.45 (m, 2 H) ppm. 13C NMR (75 MHz): δ = 28.8, 59.1, 69.5, 75.3, 85.4, 86.3, 86.8, 122.9, 128.5, 128.6, 132.0, 209.1 ppm. HRMS (EI): m/z calcd for C14H14O: 198.1045; found: 198.1040.
Compound 20A: IR: 1691 cm-1. 1H NMR (300 MHz): δ = 2.66 (m, 2 H), 3.23 (s, 2 H), 4.00 (t, 2 H, J = 5.5 Hz), 4.83 (s, 2 H), 5.99 (t, 1 H, J = 4.7 Hz), 7.25 (m, 2 H), 7.40 (m, 3 H) ppm. 13C NMR (75 MHz): δ = 33.8, 42.3, 71.7, 72.0, 128.0, 128.4, 128.5, 129.3, 131.0, 134.2, 141.5, 165.8, 203.0 ppm. HRMS (EI): m/z calcd for C15H14O2: 226.0994; found: 226.0991.
Compound 21a: IR: 1975 cm-1. 1H NMR (300 MHz): δ = 2.25 (s, 3 H), 3.69 (s, 3 H), 3.84 (td, 2 H, J = 2.5, 7.1 Hz), 4.26 (s, 2 H), 4.71 (td, 2 H, J = 2.5, 6.5 Hz), 5.01 (p, 1 H, J = 7.0 Hz), 6.67 (m, 2 H), 6.94 (m, 2 H), 7.16 (d, 2 H, J = 8.1 Hz), 7.67 (d, 2 H, J = 8.3 Hz) ppm. 13C NMR (75 MHz): δ = 21.6, 37.0, 45.9, 55.4, 76.5, 80.2, 85.7, 113.8, 114.4, 127.8, 129.6, 133.1, 136.1, 143.6, 159.7, 209.9 ppm. HRMS (EI): m/z calcd for C22H23NO3S: 381.1399; found: 381.1405.
Compound 21A: IR: 1699 cm-1. 1H NMR (300 MHz): δ = 2.41 (s, 3 H), 2.65 (dd, 2 H, J = 5.6, 11.2 Hz), 2.98 (s, 2 H), 3.62 (t, 2 H, J = 5.9 Hz), 3.86 (s, 3 H), 4.53 (s, 2 H), 5.78 (t, 1 H, J = 5.2 Hz), 6.99 (d, 2 H, J = 8.6 Hz), 7.25 (m, 4 H), 7.55 (d, 2 H, J = 8.2 Hz) ppm. 13C NMR (75 MHz): δ = 21.7, 30.9, 42.1, 49.2, 49.4, 55.5, 114.3, 122.7, 125.9, 127.2, 129.8, 130.8, 135.0, 136.5, 142.6, 143.8, 160.1, 160.6, 203.0 ppm. HRMS (EI): m/z calcd for C23H23NO4S: 409.1348; found: 409.1350.
Compound 22a: IR: 1946 cm-1. 1H NMR (300 MHz): δ = 1.75 (s, 3 H), 2.42 (s, 5 H), 3.30 (t, 2 H, J = 7.6 Hz), 3.89 (d, 2 H, J = 6.9 Hz), 4.73 (m, 2 H), 4.94 (m, 1 H), 7.30 (d, 2 H, J = 8.0 Hz), 7.71 (d, 2 H, J = 8.1 Hz) ppm. 13C NMR (75 MHz): δ = 3.7, 19.4, 21.7, 46.5, 47.4, 66.1, 75.9, 76.6, 86.2, 127.4, 129.9, 137.3, 143.5, 209.6 ppm. HRMS (EI): m/z calcd for C16H19NO2S: 289.1136; found: 289.1136.
Compound 22A: IR: 1694 cm-1. 1H NMR (300 MHz): δ = 1.36 (s, 3 H), 1.70 (s, 2 H), 2.36 (s, 3 H), 2.92 (s, 2 H), 3.37 (m, 2 H), 3.99 (d, 2 H, J = 2.4 Hz), 5.55 (t, 1 H, J = 2.4 Hz), 7.25 (d, 2 H, J = 7.9 Hz), 7.63 (d, 2 H, J = 8.0 Hz) ppm. 13C NMR (75 MHz): δ = 8.8, 21.7, 30.5, 32.5, 46.1, 50.4, 114.2, 121.3, 125.7, 127.3, 130.0, 135.8, 135.8, 136.8, 143.9, 204.0 ppm. HRMS (EI): m/z calcd for C17H19NO3S: 317.1086; found: 317.1085.