Page 13 of 23
The Journal of Organic Chemistry
δ = 7.44 (s, 1H), 7.11 (m, 1H), 6.66ꢀ6.56 (m, 2H), 5.47 (s, 1H), 4.54ꢀ4.42 (m, 1H), 3.79 (s, 3H),
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3.26ꢀ3.33 (m, 2H), 2.88 (t, J = 2.5 Hz, 1H), 2.48 (t, J = 3 Hz, 1H), 2.39 (s, 3H), 2.06ꢀ2.02 (m, 1H),
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1.98ꢀ1.96 (m, 1H), 1.69ꢀ1.67 (m, 2H), 1.23ꢀ0.97 (m, 17H); CNMR (CDCl3, 100 MHz) δ = 171.9,
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158.9, 155.2, 136.5, 133.8, 127.2, 115.3, 112.5,79.7, 60.2, 59.9, 59.1, 55.3, 52.6, 44.3, 30.9, 30.8,
30.3, 30.2, 24.4, 24.3, 22.9,21.0, 20.2, 19.8; 31P NMR (CDCl3 162 MHz): δ 14.5; HRMS (TOF ES+)
m/z calcd for C25H40N4O4P [(M + H)+], 491.2782; found, 491.2776.
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Methyl (4R,5S)-1-((3aR,7aR)-1,3-diisopropyl-2-oxidooctahydrobenzo[d][1,3,2]diazaphosphol-2-yl)
-5-(3,4-dimethoxyphenyl)-4,5-dihydro-1H-imidazole-4-carboxylate (3f)
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White solid; 233 mg ,92%; mp 97−98 °C; [α]25 D =ꢀ161 (c = 1.8, CHCl3); HNMR (CDCl3, 400
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MHz) δ = 7.34 (s, 1H), 6.81ꢀ6.73 (m, 3H), 5.05ꢀ5.02 (m, 1H), 4.67ꢀ4.62 (m, 1H), 3.80 (s, 3H), 3.79
(s, 3H), 3.69ꢀ3.66 (m, 3H), 3.22ꢀ3.20 (m, 2H), 2.88ꢀ2.85 (m, 1H), 2.50ꢀ2.47 (m, 1H), 1.97ꢀ1.95 (m,
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1H), 1.85ꢀ1.82 (m, 1H), 1.70ꢀ1.66 (m, 2H), 1.35ꢀ0.99 (m, 15H); CNMR (CDCl3, 100 MHz) δ =
171.5, 155.0, 149.3, 149.0, 135.2, 135.1, 119.7, 111.0, 109.8, 79.1, 64.1, 60.1, 60.0, 56.1, 55.9, 52.5,
44.4, 30.7, 30.3,24.4, 24.2, 22.9, 22.7,21.2, 19.7; 31P NMR (CDCl3 162 MHz): δ 15.4; HRMS (TOF
ES+) m/z calcd for C25H40N4O5P [(M + H)+], 507.2731; found, 507.2725.
Methyl (4R,5S)-1-((3aR,7aR)-1,3-diisopropyl-2-oxidooctahydrobenzo[d][1,3,2]diazaphosphol-2-yl)
-5-(4-fluorophenyl)-4,5-dihydro-1H-imidazole-4-carboxylate (3g)
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White solid; 202 mg, 87%; mp 138−139 °C; [α]25 D =ꢀ155 (c = 1.1, CHCl3); HNMR (CDCl3, 400
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MHz) δ = 7.35 (s, 1H), 7.23ꢀ6.95 (m, 4H), 5.11 (s, 1H), 4.64 (s, 1H), 3.72 (s, 3H), 3.27ꢀ3.25 (m, 1H),
3.07ꢀ3.03 (m, 1H), 2.89ꢀ2.87 (m, 1H), 2.55 (t, J = 10 Hz, 1H), 2.03ꢀ2.00 (m, 2H), 1.74ꢀ1.72 (m, 2H),
1.45ꢀ0.98 (m, 16H); 13CNMR (CDCl3, 100 MHz) δ = 171.3, 163.8, 161.3, 154.7, 138.7, 128.9, 115.7,
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79.1, 63.6, 60.2, 59.8, 52.6,44.4, 44.2, 30.8, 30.1,24.3, 24.2, 23.8, 22.7, 22.6, 21.1, 19.7; P NMR
(CDCl3 162 MHz): δ 14.2; HRMS (TOF ES+) m/z calcd for C23H35FN4O3P [(M + H)+], 465.2425;
found, 465.2428.
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