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

doi:10.1055/s-2007-967986

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Synlett 2007(3): 0453-0459
DOI: 10.1055/s-2007-967986

LETTER

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;

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Publication History

Received 8 November 2006
Publication Date:
07 February 2007 (online)

Abstract
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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

References and Notes

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10

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.