Page 17 of 29
The Journal of Organic Chemistry
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2972, 1731, 1683; HRꢀMS (ESI) m/z: [M+Na]+ Calcd for C16H19F3O5Na 371.1077; found
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371.1079; Isolated yield: 262 mg (95%) from 220 mg of 2f.
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3ꢀPentanyl 3ꢀ(3,5ꢀdifluoroꢀ4ꢀmethoxyphenyl)ꢀ3ꢀoxopropanoate, 3g. Oil; 1H NMR (400 MHz,
CDCl3) δ (ppm): keto (80%) ꢀ enol (20%) mixture, 0.86 (t, J = 7.5 Hz, 6H3), 0.93 (t, J = 7.5 Hz,
2.1H), 1.60 (m, 5H), 3.92 (s, 2H), 4.07 (t, J = 4.0 Hz), 4.12 (t, J = 4.0 Hz, 3H), 4.83 (quint, J =
6.7 Hz, 1H), 4.90 (quint, J = 6.7 Hz, 0.3H), 5.64 (s, 0.3H), 7.34 (d, J = 9.7 Hz, 0.3H), 7.53 (d, J
= 9.7 Hz, 2H), 12.64 (s, 0.3H); 19F NMR (235 MHz, CDCl3) δ (ppm): ꢀ126.9 (s, 2F), ꢀ127.8 (s,
0.5F); 13C NMR [1H] (CDCl3, 101 MHz) δ (ppm): 9.3, 9.4, 26.2, 26.4, 45.8, 61.5 (q, J = 4.0 Hz),
77.0, 78.4, 88.0, 110.0 (dd, J = 17.4 Hz, J = 7.5 Hz), 112.8 (dd, J = 17.4 Hz, J = 7.5 Hz), 127.9
(t, J = 6.3 Hz), 129.8 (t, J = 6.3 Hz), 138.6 (t, J = 13.2 Hz), 141.1 (t, J = 13.2 Hz), 156.7 (dd, J =
250.2 Hz, J = 5.9 Hz), 155.1 (dd, J = 250.2 Hz, J = 5.9 Hz), 166.7, 168.3, 172.8, 188.9 (t, J =
2.2 Hz); IR (ATR) ν (cmꢀ1): 2970, 1732, 1694; HRꢀMS (ESI) m/z: [M+Na]+ Calcd for
C15H18F2O4Na 323.1063; found 323.1065; Isolated yield: 261 mg (85%) from 250 mg of 2g.
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3ꢀPentanyl 3ꢀ(3,4ꢀdifluorophenyl)ꢀ3ꢀoxopropanoate, 3h. Oil; H NMR (360 MHz, CDCl3) δ
(ppm): keto (70%) ꢀ enol (30%) mixture, 0.85 (t, J = 7.4 Hz, 6H), 0.93 (t, J = 7.4 Hz, 2.67H),
1.55 (m, 4H), 1.65 (m, 1.50H), 3.96 (s, 2H), 4.82 (quint, J = 7.4 Hz, 1H), 4.92 (quint, J = 7.4
Hz, 0.30H), 5.62 (s, 0.24H), 7.27 (m, 1H), 7.62 (m, 0.7H), 7.82 (m, 2H), 12.69 (s, 0.26H,); 19
F
NMR (235 MHz, CDCl3) δ (ppm): ꢀ129.0 (d, J = 20.9 Hz, 1F), ꢀ133.7 (d, J = 21.1 Hz, 0.3F,
enol), ꢀ137.0 (d, J = 20.9 Hz, 1F), ꢀ137.2 (d, J = 21.1 Hz, 0.3F); 13C NMR [1H] (CDCl3, 101
MHz) δ (ppm): 9.4, 9.6, 26.3, 26.5, 46.2, 78.6, 88.2, 115.8 (d, J = 19.3 Hz), 118.2 (m), 122.5
(dd, J = 7.6 Hz, J = 3.6 Hz), 126.07 (dd, J = 7.6 Hz, J = 3.6 Hz), 133.7 (dd, J = 7.6 Hz, J = 3.7
Hz), 150.9 (dd, J = 251.5 Hz, J = 18.4 Hz), 154.4 (dd, J = 253.5 Hz, J = 18.1 Hz), 166.2, 173.4,
190.5; IR (ATR) ν (cmꢀ1): 2973, 2943, 1737, 1695; HRꢀMS (ESI) m/z: [M+Na]+ Calcd for
C14H16F2O3Na 293.0960; found 293.0955; Isolated yield: 201 mg (80%) from 200 mg of 2h.
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3ꢀPentanyl 3ꢀ(3ꢀtrifluoromethoxyꢀ4ꢀfluorophenyl)ꢀ3ꢀoxopropanoate, 3i. Oil; H NMR (360
MHz, CDCl3) δ (ppm): keto (67%) ꢀ enol (33%) mixture, 0.83 (t, J = 7.4 Hz, 6H), 0.92 (t, J =
7.4 Hz, 3H), 1.51 – 1.58 (m, 4H), 1.59 – 1.66 (m, 2H), 3.97 (s, 2H), 4.81 (quint, J = 7.4 Hz,
1H), 4.91 (quint, J = 7.3 Hz, 0.5H), 5.63 (s, 0.5H), 7.24 (t, J = 8.6 Hz, 0.5H), 7.31 (t, J = 8.6 Hz,
1H), 7.72 (m, 1H), 7.94 (m, 2H), 12.72 (s, 0.5H); 19F NMR (235 MHz, CDCl3) δ (ppm): ꢀ59.36
(d, J = 7.8 Hz, 1F), ꢀ59.42 (d, J = 6.5 Hz, 3F), ꢀ120.25 (q, J = 5.5 Hz, 1F), ꢀ124.83 (q, J = 5.5
Hz, 0.5F); 13C NMR [1H] (CDCl3, 91 MHz) δ (ppm): 9.3, 9.5, 26.2, 26.5, 46.2, 77.2, 78.6, 80.8,
117.4 (d, J = 19.3 Hz), 117.7 (d, J = 19.3 Hz), 121.8, 124.3, 126.1 (d, J = 8.5 Hz), 129.1 (d, J =
8.5 Hz), 130.8 (d, J = 3.8 Hz), 133.2 (d, J = 3.8 Hz), 136.5 (dq, J = 19.2 Hz, J = 2.8 Hz), 136.8
(dq, J = 19.2 Hz, J = 2.8 Hz), 156.1 (d, J = 258.4 Hz), 157.7 (d, J = 258.4 Hz), 166.7, 168.4,
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