Synlett 2006(13): 2099-2103  
DOI: 10.1055/s-2006-948172
LETTER
© Georg Thieme Verlag Stuttgart · New York

C-N Bond-Linked Conjugates of Dibenz[b,f][1,4]oxazepines with 2-Oxindole

Xinglong Xinga, Jinlong Wua, Jialu Luoa, Wei-Min Dai*a,b
a Laboratory of Asymmetric Catalysis and Synthesis, Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China
Fax: +86(571)87953128; e-Mail: [email protected];
b Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, P. R. of China
Fax: +85223581594; e-Mail: [email protected];
Further Information

Publication History

Received 26 April 2006
Publication Date:
09 August 2006 (online)

Abstract

An expeditious synthesis of highly functionalized dibenz[b,f][1,4]oxazepin-11(10H)-ones and dibenz[b,f][1,4]-oxazepine-11(10H)-carboxamides has been established via microwave-assisted one-pot U-4CR and intramolecular O-arylation. A Pd-catalyzed intramolecular amidation was successfully performed under microwave irradiation to furnish the novel conjugates of dibenz[b,f][1,4]oxazepin-11(10H)-ones with a 2-oxindole linked through a C-N single bond.

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14

The X-ray crystal data of 3c (excluding structure factors) have been deposited at the Cambridge Crystallographic Data Centre as supplementary publication no CCDC 605469. Copy of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK [fax: +44(1223)336033 or e-mail: [email protected]].

17

Selected Spectroscopic Data.
Compound 3c: a white crystalline solid; mp 234-235 °C (EtOAc-hexane). IR (KBr): 3422, 2929, 1647, 1344 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.73 (d, J = 2.4 Hz, 1 H), 8.22 (dd, J = 8.4, 2.8 Hz, 1 H), 7.57 (d, J = 7.6 Hz, 1 H), 7.43 (d, J = 8.0 Hz, 1 H), 7.39 (d, J = 7.6 Hz, 1 H), 7.24 (d, J = 8.8 Hz, 1 H), 7.19 (t, J = 7.6 Hz, 1 H), 7.05 (t, J = 7.6 Hz, 1 H), 6.89 (s, 1 H), 6.72 (d, J = 8.0 Hz, 1 H), 6.13 (s, 1 H), 6.01 (br s, 1 H), 3.94-3.86 (m, 1 H), 2.14 (s, 3 H), 2.02-1.93 (m, 2 H), 1.71-1.55 (m, 3 H), 1.40-1.30 (m, 2 H), 1.23-1.12 (m, 3 H). 13C NMR (100 MHz, CDCl3): δ = 167.8, 165.6, 165.4, 154.4, 145.1, 138.3, 133.7, 133.6, 132.2, 130.5, 129.2, 128.7, 127.5, 127.5, 126.8 (br), 126.1, 121.7, 121.6, 68.3 (br and very weak), 49.4, 33.1, 33.1, 31.2 (for minor atropisomer), 25.8, 25.1, 25.0, 20.9 (two carbons are missing due to atropisomerism). MS (+ESI): m/z (%) = 586 (100) [M + Na+]. Anal. Calcd for C28H26BrN3O5: C, 59.58; H, 4.64; N, 7.44. Found: C, 59.32; H, 4.63; N, 7.56.
Compound 4a: a white crystalline solid; mp 171-174 °C (EtOAc-hexane); R f = 0.25 (17% EtOAc in hexane). IR (KBr): 3280, 2929, 1654, 1522, 1345, 1266 cm-1. 1H NMR (400 MHz, CDCl3): δ = 8.18 (dd, J = 8.8, 2.4 Hz, 1 H), 8.11 (d, J = 2.8 Hz, 1 H), 7.47 (d, J = 7.6 Hz, 2 H), 7.40 (d, J = 8.8 Hz, 1 H), 7.36 (t, J = 7.6 Hz, 1 H), 7.27-7.23 (m, 2 H), 7.16 (d, J = 8.4 Hz, 1 H), 6.98 (d, J = 8.0 Hz, 1 H), 6.76 (s, 1 H), 6.40 (s, 1 H), 6.28 (br d, J = 8.0 Hz, 1 H), 3.70-3.60 (m, 1 H), 1.94 (s, 3 H), 1.88-1.84 (m, 1 H), 1.80-1.50 (m, 4 H), 1.40-1.08 (m, 5 H). 13C NMR (100 MHz, CDCl3): δ = 171.3, 166.3, 158.8, 148.9, 142.7, 135.3, 133.4, 131.5, 131.4, 130.1 (x2), 129.9 (x2), 128.9, 128.2, 127.5, 124.6, 123.8, 122.1, 121.2, 61.3, 48.4, 33.2, 32.7, 25.3, 24.6, 20.4. MS (+ESI): m/z (%) = 508 (100) [M + Na+], 486 (14) [M + H+]. Anal. Calcd for C28H27N3O5: C, 69.26; H, 5.61; N, 8.65. Found: C, 69.28; H, 5.65; N, 8.65.
Compound 5c: a white crystalline solid; mp 222-224 °C. IR (KBr): 3448, 2924, 1654, 1348 cm-1. 1H NMR (500 MHz, DMSO-d 6, 80 °C): δ = 8.42 (br s, 1 H), 8.37 (dd, J = 9.0, 3.0 Hz, 1 H), 7.59 (d, J = 9.0 Hz, 1 H), 7.30-7.26 (m, 4 H), 7.18 (d, J = 8.0 Hz, 1 H), 7.08 (br s, 1 H), 6.99 (t, J = 8.0 Hz, 1 H), 5.90-5.60 (br s, 1 H), 4.14-4.08 (m, 1 H), 2.31 (s, 3 H), 2.29-2.09 (m, 2 H), 1.89-1.70 (m, 5 H), 1.46-1.24 (m, 3 H). 13C NMR (125 MHz, DMSO-d 6, 80 °C): δ = 172.0, 164.3, 162.8 (br and weak), 152.5, 144.8, 143.2, 137.8, 131.4 (br and weak), 128.9, 128.7, 127.5, 127.5, 126.2, 125.5, 123.5 (br), 123.1 (br), 122.0, 121.8, 121.7, 109.8, 62.8 (br and weak), 52.6, 28.7, 28.4, 25.6, 25.0, 20.1. MS (+ESI): m/z 506 (100) [M + Na+]. Anal. Calcd for C28H25N3O5: C, 69.55; H, 5.21; N, 8.69. Found: C, 69.55; H, 5.23; N, 8.69.