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The Journal of Organic Chemistry
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102.0, 96.7, 95.3, 65.3, 64.9, 62.9, 54.9, 33.3. IR (film); νmax: 3600‐3100 (br), 1653, 1614, 1434, 1204, 1092, 1040.
[α]D23= +42 °(c= 0.1, MeOH).
Vinylogous carbonate 33. Phenanthrene 54a (7.1 mg, 0.046 mmol) was dissolved in DMF (1.0 mL) and added to an
argon purged flask containing trifluoroethylester 25 (6.8 mg, 0.016 mmol) and K3PO4 (9.3 mg, 0.044 mmol) and the
solution was stirred at rt for 30h. The reaction mixture was then dissolved in EtOAc (5 mL), cooled to 0 °C, acidified
with 0.5 N KHSO4, and extracted with EtOAc (3 x 5 mL). The organics were combined, dried over Na2SO4, filtered, and
concentrated to a brown oil. The oil was purified on a flash silica column (0‐20% EtOAc in CH2Cl2) to yield 33 as a
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yellow foam (6.6 mg, 56%). H NMR (500 MHz, CDCl3) δ (ppm) 17.95 (s, 1H), 10.11 (s, 1H), 8.20 (d, 1H, J = 9.5 Hz),
8.13 (d, 1H, J = 9.5 Hz), 7.10 (s, 1H), 5.18 (dd, 1H, J = 5.5, 0.9 Hz), 4.72‐4.61 (m, 2H), 4.61‐4.51 (m, 1H), 4.47‐4.44 (m,
1H), 4.00 (s, 3H), 3.91 (s, 3H), 3.75 (s, 3H), 3.18 (d, 1H, J = 3.1 Hz), 3.08‐3.01 (m, 2H), 2.28 (ddd, 1H, J = 13.9, 7.4, 4.9
Hz), 2.05‐1.98 (m, 1H), 1.76 (dq, 2H, J = 15.2, 7.4 Hz), 1.53 (s, 3H), 1.43 (s, 3H), 1.16 (t, 3H, J = 7.3 Hz). 13C NMR (100
MHz, CDCl3) δ (ppm) 166.8, 164.1, 162.7, 154.2, 152.9, 146.2, 142.7, 140.4, 138.8, 133.1, 128.4, 125.1, 124.5 (d, J= 79
Hz), 123.2, 121.2, 117.7, 117.2, 111.1, 110.4, 110.2, 109.5, 107.0, 72.7, 70.7, 63.9, 62.9, 62.8, 60.2 (q, J= 29 Hz), 33.9,
32.5, 32.1, 28.1, 26.1, 21.0, 14.1. 19 F (ppm) ‐73.6. IR (film); νmax: 2970, 2936, 2874, 2856, 1739, 1588, 1411, 12283,
1163, 1003. HRMS: m/z calcd. for C35H36ClF3NO11 (MH)+: 738.19299, found 738.1898. [α]D23= ‐34 °(c= 0.1, CHCl3).
Vinylogous carbonate 34. HFIP ester 26 (44 mg, 0.090 mmol) was dissolved in DMA (4 mL) and added to a stirring
solution of phenanthrene 5 (44 mg, 0.100 mmol) and K3PO4 (57 mg, 0.27 mmol) in DMA (3 mL) at rt. And stirred for
39h. The solution was then dissolved in EtOAc (15 mL) and a saturated solution of ammonium chloride (5 mL) was
added. The resulting solution was extracted with EtOAc (3X 15 mL). The organics were combined, dried over Na2SO4,
filtered, and concentrated under reduced pressure to afford a yellow oil foam. The foam was purified on a flash silica
column (0 to 25% EtOAc in CH2Cl2) to yield 34 as a bright yellow oil (44 mg, 61%). 1H NMR (500 MHz, CDCl3) δ (ppm)
17.98 (s, 1H), 10.14 (s, 1H), 8.18 (d, 1H, J = 9.5 Hz), 8.14 (d, 1H, J = 9.5 Hz), 7.08 (s, 1H), 5.94 (p, 1H, J = 6.1 Hz), 5.16 (d,
1H, J = 5.5 Hz), 4.59 (dt, 1H, J = 8.5, 4.5 Hz), 4.52‐4.43 (m, 1H), 3.98 (s, 3H), 3.91 (s, 3H), 3.75 (s, 3H), 3.20 (s, 1H), 3.09‐
3.02 (m, 2H), 2.25 (ddd, 1H, J = 15.5, 7.5, 4.9 Hz), 2.03 (ddd, 1H, J = 14.0, 6.5, 3.9 Hz), 1.76 (h, 2H, J = 7.3 Hz), 1.52 (s,
3H), 1.42 (s, 3H), 1.16 (t, 3H, J = 7.3 Hz).13C NMR (100 MHz, CDCl3) δ (ppm) 166.7, 165.0, 162.4, 154.2, 153.0, 148.3,
145.8, 142.7, 140.4, 138.6, 133.1, 128.4, 125.0, 123.2, 121.3, 117.6, 117.4, 110.2, 109.7, 108.0 (d, J= 216 Hz), 72.4,
70.6, 66.5 (quint, J= 27 Hz), 63.8, 63.0, 62.8, 33.3, 32.5, 32.1, 28.0, 26.0, 21.0, 14.1. 19 F (ppm) ‐73.0. IR (film); νmax:
3018, 2964, 1744, 1588, 1263, 1210, 1169, 1001. HRMS: m/z calcd. for C36H35ClF6NO11(MH)+: 806.1803, found
806.1808. [α]D23= ‐74 °(c= 0.1, CHCl3).
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