Allenic Pauson-Khand Reaction Catalyzed by Cobalt-Rhodium Hetero­bimetallic Nanoparticles

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.

allenes - alkynes - carbonylations - Pauson-Khand ­reaction - nanoparticle

References and Notes

For leading reviews, see:

1a Pauson PL. Tetrahedron  1985,  41:  5855 

1b Chung YK. Coord. Chem. Rev.  1999,  188:  297 

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2 For a review on PKR of electron-poor alkenes, see: Rodríguez Rivero M. Adrio J. Carretero C. Synlett  2005,  26 

3 For a recent review, see: Alcaide B. Almendros P. Eur. J. Org. Chem.  2004,  3377 

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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.

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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.