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C. Wang, Y. Guan
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(15) Methyl (1S,4S)-8-methoxy-1-methyl-1,2,4,5-tetrahydro-3H-
1,4-methanobenzo[d]azepine-3-carboxylate (18)
A 4 mL vial was charged with sulfinimine 17 (13 mg, 0.05
mmol, 1.0 equiv), catalyst C7 (1.5 mg, 0.0025 mmol, 0.05 equiv),
and oxidant O1 (29 mg, 0.1 mmol, 2.0 equiv). PhCF3 (0.5 mL),
previously dried in vacuo for 0.5 h, was then added and the
solution was bubbled with N2 for 10 min. PMHS (22 μL, 0.1
mmol, 2.0 equiv) was added, and the resulting mixture was
stirred at 25 °C for 20 h then diluted with EtOAc (2 mL). The
solution was washed with H2O (0.5 mL) and brine (3 × 0.5 mL),
then dried (Na2SO4) and concentrated in vacuo. The residue was
purified by preparative TLC (PE–EtOAc, 5:1) to give a yellow
solid: yield; 10.8 mg (83%); mp 89–92 °C; []D25 +167.3 (c 0.55,
CHCl3).
IR (KBr): 3795, 2957, 1701, 1612, 1495, 1453, 1389, 863, 805,
769, 741, 698 cm–1. Rotamer 1H NMR (500 MHz, CDCl3): = 7.03
(d, J = 8.4 Hz, 0.5 H), 6.99 (d, J = 8.3 Hz, 0.5 H), 6.85–6.80 (m, 1
H), 6.72 (td, J = 8.3, 2.5 Hz, 1 H), 4.50–4.43 (m, 0.6 H), 4.39–4.32
(m, 0.4 H), 3.82–3.74 (m, 3 H), 3.72–3.66 (m, 1.3 H), 3.63–3.58
(m, 1.7 H), 3.42 (d, J = 10.1 Hz, 0.5 H), 3.36 (d, J = 9.9 Hz, 0.5 H),
3.28 (d, J = 10.0 Hz, 0.5 H), 3.22 (d, J = 9.9 Hz, 0.5 H), 3.18 (d, J =
16.6 Hz, 0.5 H), 3.04 (d, J = 16.6 Hz, 0.5 H), 2.90 (d, J = 16.6 Hz, 1
H), 2.02–1.86 (m, 2 H), 1.57–1.45 (m, 3 H). 13C NMR (125 MHz,
CDCl3): = 157.9, 157.8, 155.1, 154.9, 145.8, 145.7, 130.5, 130.3,
125.7, 125.4, 111.6, 111.4, 109.89, 109.86, 61.6, 61.2, 55.29,
55.27, 54.8, 54.6, 52.2, 52.0, 42.2, 41.7, 41.6, 40.8, 36.4, 35.7,
20.8. HRMS (ESI): m/z [M + H]+ calcd for C15H20NO3: 262.1443;
found: 262.1437.
© 2021. Thieme. All rights reserved. Synlett 2021, 32, A–D