The Journal of Organic Chemistry
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53: purification by flash chromatography over silica (hexane/diethyl
ether 4/1). Yield: 55.0 mg (49%) using Λ-1P. FT-IR (ATR; ν, cm−1):
3479, 2961, 1706, 1370, 1280, 1250, 1147, 1107, 1015. 1H NMR (400
MHz, CDCl3, 300 K; δ, ppm): 2.43 (d, J = 5.6 Hz, 1H), 2.0 (m, 1H),
1.95 (s, 3H), 1.9−1.8 (m, 4H), 1.6−1.2 (m, 6H), 1.54 (s, 3H), 1.17 (s,
3H), 1.15 (s, 3H), 1.02 (s, 3H). 13C NMR (75 MHz, CDCl3, 300 K; δ,
ppm): 170.4, 85.8, 79.4, 57.3, 54.8, 53.7, 44.8, 41.2, 35.7, 33.5, 29.6,
27.9, 26.7, 25.8, 24.2, 22.7, 21.4; in agreement with those reported in
the literature.20,75 ESI-MS (m/z): 303.2 [M + Na]+.
58: purification by flash chromatography over silica (dichloro-
methane). FT-IR (ATR; ν, cm−1): 3419, 2962, 2933, 1778, 1372,
1219, 1148, 923. 1H NMR (400 MHz, CDCl3, 300 K; δ, ppm): 5.23−
5.19 (m, 1H), 2.09 (ddd, J1 = 2.7, J2 = 4.6, J3 = 12.7 Hz; 1H) 1.91−
1.82 (m, 1H), 1.72−1.66 (m, 1H), 1.62−1.46 (m, 5H), 1.28 (s, 3H),
0.94 (d, J = 7.0 Hz, 3H), 0.83 (d, J = 7.0 Hz, 3H). 13C NMR (100
MHz, CDCl3, 300 K; δ, ppm): 157, 114.6, 77.4, 71.1, 46.6, 43.8, 37.7,
31.3, 26.2, 20.6, 19.2, 16.3. HRMS (ESI-TOF, [M + Na]+): m/z calcd
for C12H19F3O3Na 291.1178, found 291.1161.
1216, 1132. H NMR (400 MHz, CDCl3, 300 K; δ, ppm): 5.39−5.35
(m, 1H), 2.07 (s, 3H), 2.00−1.92 (m, 1H) 1.86−1.79 (m, 1H), 1.77−
1.57 (m, 3H), 1.42−1.37 (m, 1H), 1.20 (s, 3H), 1.16 (s, 3H), 1.11−
0.91 (m, 2H), 0.87 (d, J = 6.7 Hz, 3H). 13C NMR (100 MHz, CDCl3,
300 K; δ, ppm): 170.7, 71.9, 71.2, 49.9, 39.4, 34.7, 28.7, 27.6, 26.6,
22.1, 22.0, 21.6. HRMS (ESI-TOF, [M + Na]+): m/z calcd for
C12H22O3Na 237.1461, found 237.1458.
68: purification by flash chromatography over silica (hexane). Yield:
15.3 mg (18%) using Λ-1P. FT-IR (ATR; ν, cm−1): 2970, 2930, 1733,
1708, 1371, 1242, 1028. 1H NMR (400 MHz, CDCl3, 300 K; δ, ppm):
5.34−3.32 (m, 1H), 2.70−2.59 (m, 1H), 2.54−2.40 (m, 2H), 2.38−
2.30 (m, 1H), 2.13 (s, 3H), 1.69−1.46 (m, 3H), 1.01 (d, J = 6.4 Hz,
3H), 0.93 (d, J = 6.4 Hz, 3H), 0.89 (d, J = 6.5 Hz, 3H). 13C NMR (100
MHz, CDCl3, 300 K; δ, ppm): 212.0, 170.4, 69.1, 49.0, 41.3, 38.9, 38.9,
29.6, 21.2, 20.6, 20.4, 13.7. HRMS (ESI-TOF, [M + Na]+): m/z calcd
for C12H20O3Na 235.1305, found 235.1303.
73: purification by flash chromatography over silica (dichloro-
methane). Yield: 31.1 mg (29%) using Λ-1P. FT-IR (ATR; ν, cm−1):
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3281, 2934, 2871, 1772, 1365, 1325, 1216, 1131, 919. H NMR (400
59. Purification by flash chromatography over silica (dichloro-
methane). FT-IR (ATR; ν, cm−1): 2965, 2937, 1780, 1717, 1372,
MHz, CDCl3, 300 K; δ, ppm): 5.62−5.59 (m, 1H), 2.08−2.02 (m,
1H) 1.90−1.84 (m, 1H), 1.79−1.61 (m, 3H), 1.53−1.48 (m, 1H), 1.22
(s, 3H), 1.19 (s, 3H), 1.07−0.90 (m, 2H), 0.90 (d, J = 6.6 Hz, 3H).
13C NMR (100 MHz, CDCl3, 300 K; δ, ppm): 156.8, 114.6, 76.1, 71.9,
50.3, 38.9, 34.5, 28.9, 27.6, 26.4, 21.9, 21.8. HRMS (ESI-TOF, [M +
Na]+): m/z calcd for C12H19F3O3Na 291.1178, found 291.1157.
74: purification by flash chromatography over silica (dichloro-
methane). Yield: 6.4 mg (6%) using Λ-1P. FT-IR (ATR; ν, cm−1):
2970, 2936, 2877, 1780, 1715, 1374, 1341, 1218, 1149, 893. 1H NMR
(400 MHz, CDCl3, 300 K; δ, ppm): 5.54 (m, 1H), 2.68−2.54 (m,
2H), 2.49−2.39 (m, 2H), 1.71−1.58 (m, 3H), 1.05 (d, J = 6.5 Hz,
3H), 0.95 (d, J = 6.4 Hz, 3H), 0.93 (d, J = 6.5 Hz, 3H). 13C NMR (100
MHz, CDCl3, 300 K; δ, ppm): 210.4, 157.0, 114.6, 74.5, 48.8, 40.9,
38.6, 38.2, 29.5, 20.5, 20.3, 13.7. HRMS (ESI-TOF, [M + Na]+): m/z
calcd for C12H17F3O3Na 289.1022, found 289.1037.
Millimole Scale Reactions. Substrate: 51 and 75. A round-bottom
flask was charged with catalyst (21 μmol, 3 mol %), alkane (0.7 mmol,
1 equiv), CH3CN (14 mL), and a magnetic stir bar. A 1.74 M
CH3CO2H solution in CH3CN was added (0.6 mL, 1.05 mmol,
150 mol %), the mixture was placed in an ice bath or an CH3CN/N2
bath, and the contents were stirred. The necessary amount of a 1.5 M
(X equiv, see Table 2) H2O2 solution (diluted from a 35% H2O2
aqueous solution) was delivered by syringe pump over 17 min at 0 or
−35 °C. After syringe pump addition, the solution was stirred for
10 min at 0 or −35 °C. Solvent was removed under reduced pressure,
and the resulting residue was purified by flash chromatography on
silica gel. If necessary, the recovered starting material was submitted to
a second oxidation using the aforementioned procedure and
employing proportional amounts of each reactant, so that the
proportions stay the same. Workup was identical with the former
procedure. If necessary, a third oxidation can be done in the same way.
76: purification of products by flash chromatography over silica
(hexane/diethyl ether from 30/1 to 1/1). Yield: 86.1 mg (48%) using
Λ-1P. FT-IR (ATR; ν, cm−1): 3340, 2948, 1717, 1478, 1283, 1140,
928, 897. 1H NMR (400 MHz, CDCl3, 300 K; δ, ppm): 5.36−5.35 (m,
1H), 1.95−1.89 (m, 1H), 1.87−1.81 (m, 1H), 1.78−1.60 (m, 3H),
1.44−39 (m, 1H), 1.22 (s, 9H), 1.20 (s, 3H), 1.16 (s, 3H), 1.11−0.91
(m, 2H), 0.88 (d, J = 6.6 Hz, 3H). 13C NMR (100 MHz, CDCl3, 300 K;
δ, ppm): 178.0, 71.9, 71.2, 49.9, 39.5, 39.0, 34.8, 28.8, 27.6, 27.2, 26.8,
22.2, 22.1. HRMS (ESI-TOF, [M + Na]+): m/z calcd for C15H28O3Na
279.1931, found 279.1909.
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1220, 1157. H NMR (400 MHz, CDCl3, 300 K; δ, ppm): 5.25 (dt,
J1 = 4.4, J2 = 10.8 Hz; 1H), 2.59 - 2.50 (m, 1H) 2.45−2.38 (m, 2H), 2.18
(dt, J3 = 1.1, J4 = 13.7 Hz; 1H), 2.12 - 2.02 (m, 2H), 1.95 - 1.88 (m,
1H), 1.07 (d, J = 1.07 Hz, 3H), 0.91 (d, J = 7.0 Hz, 3H), 0.85 (d, J =
6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3, 300 K; δ, ppm): 209.6,
157.2, 114.4, 76.0, 47.3, 41.7, 38.2, 38.0, 26.5, 20.1, 15.5, 14.0. HRMS
(ESI-TOF, [M + Na]+): m/z calcs for C12H17F3O3Na 289.1022, found
289.1045.
61: purification by flash chromatography over silica (hexane/ethyl
acetate 90/10). Yield: 44.8 mg (52%) using Λ-2P. FT-IR (ATR; ν,
cm−1): 3423, 2960, 2938, 2872, 1739, 1717, 1370, 1257, 1023, 790. 1H
NMR (400 MHz, CDCl3, 300 K; δ, ppm): 4.82 (td, J = 9.8, 4.3 Hz,
1H), 2.05 (s, 3H), 1.98 (ddd, J = 12.3, 4.3, 2.0, 1H), 1.85−1.77 (m,
1H), 1.73−1.66 (m, 2H), 1.55−1.37 (m, 3H), 1.26 (s, 3H), 1.23−1.14
(m, 1H), 0.93 (d, J = 6.7 Hz, 3H), 0.81 (d, J = 6.9 Hz, 3H). 13C NMR
(100 MHz, CDCl3, 300 K; δ, ppm): 170.4, 72.0, 70.8, 46.5, 44.5, 38.5,
26.8, 26.0, 21.3, 20.8, 20.2, 17.0. HRMS (ESI-TOF, [M + Na]+): m/z
calcd for C12H22O3Na 237.1461, found 237.1466.
62: purification by flash chromatography over silica (hexane/ethyl
acetate 90/10). Yield: 9.1 mg (11%) using Λ-2P. FT-IR (ATR; ν,
cm−1): 2961, 2928, 2872, 1714, 1365, 1235, 1030, 803. 1H NMR (400
MHz, CDCl3, 300 K; δ, ppm): 5.23 (q, J = 3.6 Hz, 1H), 2.69−2.62 (m,
2H), 2.39 (dd, J = 14.2, 4.8 Hz, 1H), 2.12 (s, 3H), 1.92−1.88 (m, 1H),
1.74 (ddd, J = 14.7, 11.8, 3.2 Hz, 1H), 1.48−1.39 (m, 1H), 1.28−1.22
(m, 1H), 1.05 (d, J = 6.7 Hz, 3H), 0.96 (d, J = 6.8 Hz, 3H), 0.94 (d,
J = 6.8 Hz, 3H). 13C NMR (100 MHz, CDCl3, 300 K; δ, ppm): 212.5,
170.4, 70.3, 48.0, 40.1, 39.1, 35.6, 28.6, 21.4, 20.3, 20.1, 14.4. HRMS
(ESI-TOF, [M + Na]+): m/z calcd for C12H20O3Na 235.1305, found
235.1309.
64: purification by flash chromatography over silica (hexane). Yield:
66.2 mg (65%) using Δ-1P. FT-IR (ATR; ν, cm−1): 3310, 2960, 2937,
2871, 1720, 1167, 1153, 1127. 1H NMR (400 MHz, CDCl3, 300 K; δ,
ppm): 4.81 (td, J = 9.3, 4.1 Hz, 1H), 1.98−1.92 (m, 1H), 1.87−1.77
(m, 1H), 1.75−1.64 (m, 2H), 1.55−1.39 (m, 3H), 1.28−1.22 (m, 1H),
1.25 (s, 3H), 1.19 (s, 9H), 0.94 (d, J = 6.9 Hz, 3H), 0.81 (d, J = 6.9
Hz, 3H). 13C NMR (100 MHz, CDCl3, 300 K; δ, ppm): 177.7, 71.9,
70.7, 46.3, 43.8, 38.8, 38.2, 27.2, 27.1, 26.0, 20.9, 19.9, 17.2. HRMS
(ESI-TOF, [M + Na]+): m/z calcd for C15H28O3Na 279.1931, found
279.1918.
65: purification by flash chromatography over silica (hexane). Yield:
9.4 mg (9%) using Δ-1P. FT-IR (ATR; ν, cm−1): 2959, 2932, 2873,
1718, 1283, 1152, 1122. 1H NMR (400 MHz, CDCl3, 300 K; δ, ppm):
5.20 (dd, J = 7.1, 3.5 Hz, 1H), 2.70−2.58 (m, 2H), 2.41 (dd, J = 14.1,
4.4 Hz, 1H), 2.15−2.09 (m, 1H), 1.93−1.71 (m, 3H), 1.25 (s, 9H),
0.96 (d, J = 6.7, 3H), 0.93 (d, J = 7.0, 3H). 13C NMR (100 MHz,
CDCl3, 300 K; δ, ppm): 212.4, 177.7, 69.9, 48.0, 40.2, 39.2, 35.5, 28.7,
27.1, 27.0, 20.3, 20.2,14.5. HRMS (ESI-TOF, [M + Na]+): m/z calcd
for C15H26O3Na 277.1774, found 277.1762.
77: purification of products by flash chromatography over silica
(hexane/diethyl ether from 30/1 to 1/1). Yield: 51.6 mg (29%) using
Δ-1P. FT-IR (ATR; ν, cm−1): 2963, 2930, 2871, 1708, 1476, 1285,
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1156, 1127. H NMR (400 MHz, CDCl3, 300 K; δ, ppm): 5.27 (m,
1H), 2.62−2.49 (m, 2H), 2.44−2.30 (m, 2H), 1.60−1.50 (m, 3H),
1.25 (s, 9H), 1.01 (d, J = 6.6 Hz, 3H), 0.92 (d, J = 6.9 Hz, 3H), 0.88
(d, J = 6.5 Hz, 3H). 13C NMR (100 MHz, CDCl3, 300 K; δ, ppm):
212.0, 177.7, 68.7, 49.3, 41.7, 39.3, 38.9, 38.8, 29.8, 27.2, 20.6, 20.5,
13.9. HRMS (ESI-TOF, [M + Na]+): m/z calcd for C15H26O3Na
277.1774, found 277.1758.
67: purification by flash chromatography over silica (hexane). Yield:
20.6 mg (24%) using Λ-1P. FT-IR (ATR; ν, cm−1): 3420, 2928, 1737,
1431
dx.doi.org/10.1021/jo302196q | J. Org. Chem. 2013, 78, 1421−1433