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TANG ET AL.
13C NMR (151 MHz, CDCl3) δ = 155.15, 147.61, 133.52,
1H NMR (600 MHz, CDCl3) δ 7.86‐7.67 (m, 4H), 7.35
(d, J = 6.8 Hz, 2H), 7.21‐7.16 (m, 2H), 7.13 (t,
J = 7.5 Hz, 2H), 3.02 (s, 2H), 2.76 (s, 1H), 1.67 (d,
J = 32.0 Hz, 3H), 1.30 (s, 3H), 1.20 (d, J = 17.2 Hz, 7H),
1.07 (s, 12H), 0.68 (d, J = 6.3 Hz, 6H).
133.27, 130.58, 129.22, 128.74, 127.98, 127.45, 125.93,
125.55, 124.88, 124.59, 119.75, 60.56, 49.77, 30.98, 27.79.
HRMS (ESI+) m/z [M + Na]: calcd. 707.3087, found
707.3091.
13C NMR (151 MHz, CDCl3) δ = 146.23, 134.08, 131.66,
131.12, 129.53, 127.78, 127.08, 125.49, 121.80, 31.80, 30.34,
29.47, 29.17, 29.03, 22.57.
2.1.15 | Synthesis of PA 1, PA 2, PA 3, PA 4,
PA 5, PA 6, PA 7, PA 8, PA 9, PA 10, PA 11,
and PA 12
HRMS (ESI+) m/z [M + Na]: calcd. 595.2922, found
595.2947.
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PA 5: 95% yield, [α]D = −83.2 (c = 0.6, CHCl3).
1H NMR (600 MHz, DMSO) δ = 8.04‐7.94 (m, 4H),
7.47‐7.42 (m, 2H), 7.31‐7.20 (m, 2H), 7.10 (d, J = 8.5 Hz,
2H), 5.90 (ddd, J = 15.8, 10.5, 5.3 Hz, 1H), 5.27 (dd,
J = 17.2, 1.3 Hz, 1H), 5.16 (d, J = 10.4 Hz, 1H), 4.46 (d,
J = 5.1 Hz, 2H), 3.99 (s, 1H), 3.21‐2.95 (m, 4H), 2.93‐
2.71 (m, 2H), 2.00‐1.71 (m, 4H), 1.02 (t, J = 7.3 Hz, 3H).
13C NMR (101 MHz, DMSO) δ = 156.44, 147.77, 134.43,
133.92, 131.13, 129.42, 128.45, 126.44, 126.18, 125.64,
122.00, 117.34, 64.61, 32.67, 29.46, 27.57, 22.58, 14.53.
HRMS (ESI+) m/z [M + Na]: calcd. 554.1687, found
554.1702.
11c (30 mg, 0.07 mmol, 1.0 Eq) in dry DCM (10 mL),
POCl3 (14 uL, 0.15 mmol, 2.21 Eq), and Et3N (0.3 mL,
2.10 mmol, 30.0 Eq) were added at rt under nitrogen,
and the solution was stirred for 8 hours. Evaporation in
vacuo and addition of THF/H2O (1:1, 5/5 mL) provided
a mixture, which was stirred overnight at 50°C. After
the reaction reached rt, DCM was added to the reaction.
The resulting organic phase was thoroughly washed with
2 M HCl three times. The resulting organic layer was
dried over Na2SO4 and recrystallized from n‐hexane and
DCM to afford compound PA 3 (32 mg, 91%) as a yellow
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20
material. [α]D = −172.8 (c = 1.0, CHCl3).
PA 6: 92% yield, [α]D = −136.9 (c = 1.3, CHCl3).
1H NMR (600 MHz, CDCl3) δ = 7.80 (d, J = 8.2 Hz, 2H),
7.71 (s, 2H), 7.37 (t, J = 7.5 Hz, 2H), 7.25 (d, J = 8.5 Hz, 2H),
7.18‐7.14 (m, 2H), 6.18 (s, 1H), 3.19 (d, J = 13.3 Hz, 2H),
2.43 (d, J = 13.4 Hz, 2H), 0.88 (s, 18H).
1H NMR (600 MHz, CDCl3) δ = 9.25 (s, 1H), 7.90‐7.82
(m, 4H), 7.44 (t, J = 7.4 Hz, 2H), 7.28 (s, 2H), 7.24‐7.19
(m, 2H), 3.16‐3.04 (m, 2H), 2.89 (d, J = 6.0 Hz, 2H),
1.70 (s, 6H), 0.95 (d, J = 19.6 Hz, 12H).
13C NMR (151 MHz, CDCl3) δ = 146.39, 132.64, 131.39,
131.18, 127.93, 126.96, 125.87, 125.55, 121.92, 43.66, 32.70,
29.51.
13C NMR (151 MHz, CDCl3) δ = 145.11, 133.24, 130.70,
130.06, 128.53, 126.73, 126.04, 124.54, 120.76, 37.62, 27.30,
26.87, 21.61, 21.38.
HRMS (ESI+) m/z [M + Na]: calcd. 511.2006, found
511.2008.
HRMS (ESI+) m/z [M + Na]: calcd. 511.1997, found
511.2008.
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PA 1: 91% yield, [α]D = −208.0 (c = 1.2, CHCl3).
PA 7: 90% yield, [α]D = −220.4 (c = 1.5, CHCl3).
1H NMR (600 MHz, CDCl3) δ = 8.11 (s, 2H), 7.77 (d,
J = 8.1 Hz, 2H), 7.29 (dd, J = 11.0, 3.9 Hz, 2H), 7.26‐7.20
(m, 2H), 7.04 (d, J = 8.4 Hz, 2H), 5.62 (s, 1H), 3.44 (s, 2H).
13C NMR (101 MHz, CDCl3) δ = 134.26, 130.95, 129.55,
127.22, 125.99, 124.80, 120.77, 114.50, 30.90, 28.34, 21.67,
13.11.
1H NMR (600 MHz, CDCl3) δ = 8.00 (s, 1H), 7.82‐7.72
(m, 4H), 7.35 (t, J = 7.5 Hz, 2H), 7.18 (t, J = 8.4 Hz, 2H),
7.13 (dd, J = 11.4, 4.0 Hz, 2H), 3.07‐2.95 (m, 2H), 2.84‐
2.69 (m, 2H), 1.79‐1.59 (m, 4H), 1.40‐1.20 (m, 10H), 0.75
(t, J = 7.2 Hz, 6H), 0.70 (t, J = 6.6 Hz, 6H).
13C NMR (151 MHz, CDCl3) δ = 146.02, 134.40, 131.78,
131.07, 129.55, 127.77, 127.05, 125.61, 121.78, 40.24, 32.50,
27.74, 25.35, 25.13, 10.88, 10.65.
HRMS (ESI+) m/z [M + Na]: calcd. 419.0429, found
419.0443.
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PA 2: 89% yield, [α]D = −281.3 (c = 0.8, CHCl3).
HRMS (ESI+) m/z [M + Na]: calcd. 567.2630, found
567.2634.
1H NMR (400 MHz, DMSO) δ = 8.01 (d, J = 8.1 Hz,
2H), 7.93 (s, 2H), 7.46 (t, J = 7.4 Hz, 2H), 7.31‐7.21 (m,
2H), 7.13 (d, J = 8.5 Hz, 2H), 6.20 (ddt, J = 16.9, 10.0,
6.8 Hz, 2H), 5.29‐5.06 (m, 4H), 4.65 (s, 1H), 3.74 (ddd,
J = 62.8, 15.9, 6.7 Hz, 4H).
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PA 8: 89% yield, [α]D = −253.8 (c = 0.8, CHCl3).
1H NMR (600 MHz, CDCl3) δ = 7.87‐7.68 (m, 4H),
7.36 (t, J = 7.5 Hz, 2H), 7.18 (t, J = 7.8 Hz, 3H), 7.15‐
7.11 (m, 2H), 3.24‐2.94 (m, 2H), 2.76 (dd, J = 20.4,
10.6 Hz, 2H), 1.64 (dddd, J = 29.9, 24.2, 15.8, 9.7 Hz,
8H), 0.97‐0.92 (m, 2H), 0.88‐0.80 (m, 12H), 0.70 (dd,
J = 15.6, 6.7 Hz, 12H).).
13C NMR (151 MHz, DMSO) δ = 147.01, 136.13,
132.06, 130.70, 129.06, 128.01, 125.94, 125.29, 121.57,
116.79, 34.44.
13C NMR (151 MHz, CDCl3) δ = 146.04, 134.37, 131.75,
131.11, 129.65, 127.79, 127.03, 125.62, 121.86, 49.81, 31.81,
29.60, 29.25, 27.57, 21.38, 19.37, 18.97.
HRMS (ESI+) m/z [M + Na]: calcd. 451.1071, found
451.1069.
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PA 4: 90% yield, [α]D = −256.0 (c = 1.2, CHCl3).