Organic & Biomolecular Chemistry
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CHCl3); H NMR (400 MHz, CDCl3) δ 7.76 (d, J = 7.6 Hz, 1H), 3H), 3.59–3.36 (m, 2H), 3.25 (d, J = 14.1 Hz, 1H), 3.06 (d, J =
7.56 (ddd, J = 8.4, 7.3, 1.2 Hz, 1H), 7.47–7.32 (m, 2H), 17.2 Hz, 1H), 2.10 (dd, J = 32.9, 3.1 Hz, 9H), 1.63 (t, J = 3.0 Hz,
7.27–7.09 (m, 5H), 3.74 (s, 3H), 3.65 (d, J = 17.4 Hz, 1H), 3.52 6H). 13C NMR (101 MHz, CDCl3) δ 200.67, 169.68, 165.52,
(d, J = 14.0 Hz, 1H), 3.31 (d, J = 14.0 Hz, 1H), 3.20 (d, J = 156.48, 137.12, 130.00, 128.61, 128.17, 126.55, 126.20, 115.55,
17.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 202.14, 171.22, 109.19, 81.98, 62.76, 55.60, 40.98, 39.30, 36.09, 35.61, 30.82.
153.17, 136.31, 135.35, 135.13, 129.96, 128.31, 127.66, 126.85, HPLC conditions: Chiralcel AD-H column (250 × 4.6 mm),
126.24, 124.70, 61.69, 52.92, 39.77, 35.38. HPLC conditions: hexane/i-PrOH = 90/10, 1 mL min−1, 254 nm, τR (major) =
Chiralcel AS-H column (250 × 4.6 mm), hexane/i-PrOH = 99/1, 14.9 min, τR (minor) = 10.3 min. HRMS calcd for [C28H30O4 +
1 mL min−1, 254 nm, τR (major) = 19.2 min, τR (minor) = Na]+ requires m/z 453.2042, found m/z 453.2045.
16.9 min. HRMS calcd for [C18H16O3 + Na]+ requires m/z
303.0997, found m/z 303.0995.
(S)-1-Adamantyl
2-benzyl-6-methyl-1-oxo-2,3-dihydro-1H-
indene-2-carboxylate (4l). (White wax, 92% yield, 97% ee); [α]D25
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(S)-1-Adamantyl
2-benzyl-5-fluorine-1-oxo-2,3-dihydro-1H- 88.5 (c 0.64, CHCl3); H NMR (400 MHz, CDCl3) δ 7.52 (s, 1H),
indene-2-carboxylate (4h). (White solid, m. p. 165–168 °C; 95% 7.31 (d, J = 1.7 Hz, 1H), 7.24–7.08 (m, 6H), 3.58–3.37 (m, 2H),
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yield, 94% ee); [α]2D5 112.2 (c 0.23, CHCl3); H NMR (400 MHz, 3.24 (d, J = 14.1 Hz, 1H), 3.05 (d, J = 17.0 Hz, 1H), 2.35 (s, 3H),
CDCl3) δ 7.74 (dd, J = 8.3, 5.3 Hz, 1H), 7.25–7.08 (m, 5H), 2.06 (dd, J = 38.1, 4.5 Hz, 9H), 1.61 (d, J = 3.1 Hz, 6H). 13C
7.07–6.93 (m, 2H), 3.55 (d, J = 17.4 Hz, 1H), 3.43 (d, J = NMR (101 MHz, CDCl3) δ 202.77, 169.56, 150.82, 137.31,
14.0 Hz, 1H), 3.30 (d, J = 14.1 Hz, 1H), 3.11 (d, J = 17.4 Hz, 1H), 137.01, 136.32, 135.59, 130.02, 128.17, 126.56, 125.75, 124.40,
2.15–2.03 (m, 9H), 1.64 (t, J = 3.1 Hz, 6H). 13C NMR (101 MHz, 82.00, 62.85, 40.97, 39.31, 36.09, 35.32, 30.82, 21.06. Chiralcel
CDCl3) δ 200.85, 169.16, 168.52, 165.97, 156.38, 156.28, 136.63, AD-H column (250 × 4.6 mm), hexane/i-PrOH = 80/20, 1.2 mL
131.86, 131.85, 129.97, 128.26, 126.80, 126.73, 126.69, 115.82 min−1, 254 nm, τR (major) = 5.5 min, τR (minor) = 4.3 min.
(d, J = 23.9 Hz), 112.81 (d, J = 22.4 Hz), 82.32, 62.84, 40.97, HRMS calcd for [C28H30O3 + Na]+ requires m/z 437.2093, found
39.21, 36.05, 35.52, 35.50, 30.82. 19F NMR (376 MHz, CDCl3) m/z 437.2091.
δ −102.06 (s, 1F). HPLC conditions: Chiralcel AD-H column
(S)-1-Adamantyl 2-benzyl-5,6-dimethoxyl-1-oxo-2,3-dihydro-
(250 × 4.6 mm), hexane/i-PrOH = 90/10, 1 mL min−1, 254 nm, 1H-indene-2-carboxylate (4m). (Yellow wax, 81% yield, 98% ee);
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τR (major) = 7.9 min, τR (minor) = 6.5 min. HRMS calcd for [α]2D5 134.6 (c 0.65, CHCl3); H NMR (400 MHz, CDCl3) δ 7.16
[C27H27FO3 + Na]+ requires m/z 441.1842, found m/z 441.1845.
(d, J = 10.2 Hz, 6H), 6.76 (s, 1H), 3.91 (d, J = 7.1 Hz, 6H),
(S)-1-Adamantyl 2-benzyl-5-chloro-1-oxo-2,3-dihydro-1H-indene- 3.55–3.36 (m, 2H), 3.27 (d, J = 14.1 Hz, 1H), 3.02 (d, J =
2-carboxylate (4i). (White solid, m. p. 164–167 °C; 96% yield, 16.9 Hz, 1H), 2.20–2.03 (m, 9H), 1.64 (d, J = 3.1 Hz, 6H). 13C
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93% ee); [α]2D5 87.8 (c 0.26, CHCl3); H NMR (400 MHz, CDCl3) NMR (101 MHz, CDCl3) δ 201.22, 169.79, 155.68, 149.42,
δ 7.66 (d, J = 8.2 Hz, 1H), 7.36–7.28 (m, 2H), 7.17 (q, J = 7.2, 149.00, 137.08, 129.98, 128.14, 128.12, 126.55, 106.97, 104.77,
6.5 Hz, 5H), 3.54 (d, J = 17.4 Hz, 1H), 3.42 (d, J = 14.1 Hz, 1H), 81.96, 62.77, 56.18, 56.05, 40.99, 36.09, 30.81. Chiralcel AD-H
3.30 (d, J = 14.1 Hz, 1H), 3.10 (d, J = 17.4 Hz, 1H), 2.15–2.02 column (250 × 4.6 mm), hexane/i-PrOH = 80/20, 1.2 mL min−1
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(m, 9H), 1.63 (t, J = 3.1 Hz, 6H). 13C NMR (101 MHz, CDCl3) 254 nm, τR (major) = 9.9 min, τR (minor) = 8.4 min. HRMS
δ 201.34, 169.07, 154.82, 141.52, 136.55, 133.96, 129.98, calcd for [C29H32O5 + Na]+ requires m/z 483.2147, found m/z
128.29, 126.78, 126.34, 125.51, 82.38, 62.70, 40.97, 39.18, 483.2150.
36.04, 35.33, 30.82. HPLC conditions: Chiralcel AD-H column
(S)-Methyl-1-benzyl-2-oxocyclopentane-1-carboxylate
(4n).
(250 × 4.6 mm), hexane/i-PrOH = 90/10, 1 mL min−1, 254 nm, (Colorless oil, 78% yield, 54% ee); [α]D25 7.86 (c 0.49, CHCl3); 1H
τR (major) = 7.9 min, τR (minor) = 6.6 min. HRMS calcd for NMR (400 MHz, CDCl3) δ 7.34–7.24 (m, 3H), 7.14 (dd, J = 7.9,
[C27H27ClO3 + Na]+ requires m/z 457.1546, found m/z 457.1548. 1.6 Hz, 2H), 3.74 (s, 3H), 3.23 (d, J = 13.7 Hz, 1H), 3.13 (d, J =
(S)-1-Adamantyl 2-benzyl-5-chloro-1-oxo-2,3-dihydro-1H-indene- 13.7 Hz, 1H), 2.56–2.29 (m, 2H), 2.13–1.86 (m, 3H), 1.62 (dd,
2-carboxylate (4j). (White wax, 91% yield, 96% ee); [α]2D5 95.2 J = 8.8, 5.4 Hz, 1H). 13C NMR (101 MHz, CDCl3) δ 214.86,
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(c 0.32, CHCl3); H NMR (400 MHz, CDCl3) δ 7.68 (dd, J = 7.7, 171.37, 136.51, 130.14, 128.41, 126.89, 61.52, 52.67, 39.16,
2.0 Hz, 2H), 7.27–7.10 (m, 6H), 3.53 (d, J = 17.7 Hz, 1H), 3.44 38.39, 31.69, 19.46. HPLC conditions: Chiralcel AD-H column
(d, J = 14.0 Hz, 1H), 3.30 (d, J = 14.0 Hz, 1H), 3.07 (d, J = (250 × 4.6 mm), hexane/i-PrOH = 98/2, 0.6 mL min−1, 254 nm,
17.7 Hz, 1H), 2.20–2.01 (m, 9H), 1.64 (t, J = 3.1 Hz, 6H). τR (major) = 13.4 min, τR (minor) = 13.9 min. HRMS calcd for
13C NMR (101 MHz, CDCl3) δ 202.05, 168.88, 152.99, 137.73, [C14H16O3 + Na]+ requires m/z 255.0997, found m/z 255.0992.
137.41, 136.35, 129.97, 129.21, 128.29, 126.78, 123.25, 121.59,
(S)-1-Adamantyl 2-benzyl-1-oxo-1,2,3,4-tetrahydronaphtha-
82.47, 62.74, 40.96, 39.32, 36.84, 36.05, 30.83. HPLC con- lene-2-carboxylate (4o). (White wax, 89% yield, 79% ee); [α]D25
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ditions: Chiralcel AD-H column (250 × 4.6 mm), hexane/ –4.4 (c 0.81, CHCl3); H NMR (400 MHz, CDCl3) δ 8.08 (dd, J =
i-PrOH = 90/10, 1 mL min−1, 254 nm, τR (major) = 6.9 min, 7.9, 1.5 Hz, 1H), 7.48–7.40 (m, 1H), 7.34–7.14 (m, 7H), 3.51 (d,
τR (minor) = 5.4 min. HRMS calcd for [C27H27BrO3 + Na]+ J = 13.6 Hz, 1H), 3.25 (d, J = 13.7 Hz, 1H), 3.12 (ddd, J = 17.1,
requires m/z 501.1041, found m/z 501.1044.
12.1, 4.8 Hz, 1H), 2.92–2.76 (m, 1H), 2.43 (ddd, J = 13.7, 4.8,
(S)-1-Adamantyl
2-benzyl-5-methoxyl-1-oxo-2,3-dihydro-1H- 3.2 Hz, 1H), 2.27–2.07 (m, 4H), 1.99–1.91 (m, 6H), 1.61 (d, J =
indene-2-carboxylate (4k). (Light yellow solid, m. p. 133–135 °C; 3.0 Hz, 6H). 13C NMR (101 MHz, CDCl3) δ 195.05, 170.43,
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94% yield, 98% ee); H NMR (400 MHz, CDCl3) δ 7.67 (d, J = 142.87, 136.92, 133.07, 132.81, 130.96, 128.55, 127.97, 127.84,
8.5 Hz, 1H), 7.19 (d, J = 3.2 Hz, 5H), 6.91–6.69 (m, 2H), 3.84 (s, 126.55, 82.34, 59.18, 40.97, 39.60, 36.01, 30.86, 30.76, 26.20.
This journal is © The Royal Society of Chemistry 2019
Org. Biomol. Chem., 2019, 17, 573–584 | 581