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The Journal of Organic Chemistry
determined by HPLC analysis (Daicel Chiralpak AD-H column, n-hexane/i-propanol = 80:20, flow rate
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1.0 mL/min, detection at 254 nm, 35 C): t = 7.1 min (minor), t = 9.0 min (major), 92% ee. H NMR
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(400 MHz, d6-acetone) δ 10.45 (br s, 1H), 8.07 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.62 (s,
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H), 7.51 (t, J = 7.6 Hz, 1H), 7.44 (t, J = 7.2 Hz, 2H), 7.29 (d, J = 8.0 Hz, 1H), 6.91 (d, J = 8.4 Hz, 1H),
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.90 (d, J = 1.6 Hz, 1H), 2.25 (s, 3H) ppm. C{ H} NMR (100 MHz, d6-acetone) δ 172.5, 154.2, 136.3,
136.0, 129.1, 127.0, 126.7, 126.4, 125.75, 125.74 (q, J = 285.3 Hz), 124.3, 124.2, 122.7, 121.2, 112.1,
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11.4, 78.2 (q, J = 30.5 Hz), 21.6 ppm. F NMR (376.5 MHz, d6-acetone) δ -76.5 ppm. HRMS (ESI)
+
m/z: [M + Na] Calcd for C H F N NaOS 385.0598; Found 385.0608.
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(R)-1-(Benzo[d]thiazol-2-yl)-2,2,2-trifluoro-1-(6-methyl-1H-indol-3-yl)ethan-1-ol (3ac). White solid,
m.p. 145-146 C, 68.6 mg, 95% yield. [α]D10: −51.8 (c = 0.50, acetone). The enantioselectivity was
o
determined by HPLC analysis (Daicel Chiralpak AD-H column, n-hexane/i-propanol = 80:20, flow rate
o
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.0 mL/min, detection at 254 nm, 35 C): t = 12.6 min (minor), t = 15.1 min (major), 97% ee. H NMR
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(400 MHz, d6-acetone) δ 10.43 (s, 1H), 8.09 (d, J = 8.0 Hz, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.61 (s, 2H),
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.52-7.45 (m, 3H), 7.23 (s, 1H ), 6.91 (s, 1H ), 6.80 (d, J = 8.4 Hz, 1H), 2.35 (s, 3H ) ppm. C{ H}
NMR (100 MHz, d6-acetone) δ 172.4, 154.0, 137.9, 136.2, 132.1, 126.8, 126.2, 125.6 (q, J = 285.6 Hz),
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24.9, 124.2, 124.0, 122.6, 122.0, 121.1, 112.1, 111.7, 78.0 (q, J = 30.4 Hz), 21.4 ppm. F NMR (376.5
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MHz, d6-acetone) δ -76.4 ppm. HRMS (ESI) m/z: [M + Na] Calcd for C H F N NaOS 385.0598;
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Found 385.0608.
(R)-1-(Benzo[d]thiazol-2-yl)-2,2,2-trifluoro-1-(7-methyl-1H-indol-3-yl)ethan-1-ol (3ad). White solid,
m.p. 163-164 C, 72.0 mg, 99% yield. [α]D10: −42.1 (c = 0.50, acetone). The enantioselectivity was
o
determined by HPLC analysis (Daicel Chiralpak AD-H column, n-hexane/i-propanol = 80:20, flow rate
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.0 mL/min, detection at 254 nm, 35 C): t = 7.7 min (minor), t = 14.0 min (major), 97% ee. H NMR
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(400 MHz, d6-acetone) δ 10.55 (br s, 1H), 8.05 (d, J = 8.0 Hz, 1H), 7.99 (d, J = 8.0 Hz, 1H), 7.66 (s,
1H), 7.50 (t, J = 8.0 Hz, 1H), 7.43 (t, J = 8.0 Hz, 2H), 6.96 (s, 1H), 6.89 (d, J = 7.2 Hz, 1H), 6.85 (t, J =
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.2 Hz, 1H), 2.43 (s, 3H) ppm. C{ H} NMR (100 MHz, d6-acetone) δ 172.3, 153.9, 136.9, 136.1,
26.8, 126.2, 125.9, 125.5 (q, J = 285.3 Hz), 125.0, 124.0, 123.0, 122.5, 121.5, 120.4, 119.0, 112.2, 78.0
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(
q, J = 30.3 Hz), 16.6 ppm. F NMR (376.5 MHz, d6-acetone) δ -76.3 ppm. HRMS (ESI) m/z: [M +
+
Na] Calcd for C H F N NaOS 385.0598; Found 385.0595.
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(R)-1-(Benzo[d]thiazol-2-yl)-2,2,2-trifluoro-1-(4-methyl-1H-indol-3-yl)ethan-1-ol (3ae). White solid,
m.p. 207-208 C, 54.7 mg, 75% yield. [α]D10: −10.3 (c = 0.52, acetone). The enantioselectivity was
o
determined by HPLC analysis (Daicel Chiralpak AD-H column, n-hexane/i-propanol = 85:15, flow rate
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.0 mL/min, detection at 254 nm, 35 C): t = 7.7 min (minor), t = 11.2 min (major), >99% ee. H NMR
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(400 MHz, d6-acetone) δ 10.65 (br s, 1H), 8.02 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.65 (s,
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H), 7.49-7.40 (m, 2H), 7.29 (d, J = 8.0 Hz, 1H), 6.96 (t, J = 8.0 Hz, 1H), 6.68-6.65 (m, 2H), 2.94 (s,
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1
3H) ppm. C{ H} NMR (100 MHz, d6-acetone) δ 172.2, 153.4, 138.3, 137.3, 131.1, 126.9, 126.5,
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