Highly diastereoselective synthesis of dispiro[1,4-dithiane/dithiepane] bisoxindoles via Stevens rearrangement

Tetrahedron Letters

Volumn 54, Issue 50, 2013, Pages 6886-6888

  Muthusamy, Sengodagounder ^a   Selvaraj, Karuppu ^a  

^a BHARATHIDASAN UNIVERSITY   (India)

Author keywords

Diastereoselectivity; Diazo compound; Dispirodithiane; Rhodium(II) acetate; Stevens rearrangement; Sulfonium ylide

Indexed keywords

1,3 DITHIANEOXINDOLE DERIVATIVE; 3 DIAZO 2 OXINDOLE DERIVATIVE; ACETIC ACID DERIVATIVE; DISPIRO[1,4 DITHIANE]BISOXINDOLE DERIVATIVE; DISPIRO[1,4 DITHIEPANE]BISOXINDOLE DERIVATIVE; INDOLE DERIVATIVE; RHODIUM DERIVATIVE; SPIRO 1,3 DITHIOLANEOXINDOLE; SULFONIUM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; CHEMICAL REACTION; DRUG STRUCTURE; DRUG SYNTHESIS; PHARMACOLOGICAL PROCEDURES; STEREOSELECTIVITY; STEVENS REARRANGEMENT;

EID: 85013254006     PISSN: 00404039     EISSN: 18733581     Source Type: Journal    
DOI: 10.1016/j.tetlet.2013.10.030     Document Type: Article

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23. General procedure: A mixture of N-substituted spiro-1,3-dithiolaneoxindole 2a-e or spiro-1,3-dithianeoxindole 2e, 2f (1 mmol) and rhodium(II) acetate dimer (2.9 mg, 0.56 mol %) catalyst was taken in dry CH2Cl2 (20 ml) and stirred under argon atmosphere. A solution of N-substituted 3-diazoindol-2-ones 1a-d (1.2 mmol) in dry CH2Cl2 (10 ml) was added dropwise with the help of syringe pump over 1 h duration and further stirred at room temperature for the appropriate duration. The reaction was monitored using TLC. After the completion of reaction, the solvent was removed under reduced pressure. The residue was subjected to column chromatography (silica gel, 100–200 mesh, EtOAc/hexane 70:30) to furnish the ring enlarged product of dispiro-dithianes or -dithiepanes 3a-m.
24. All the new compounds exhibited spectral data consistent with their structures. Synthesis of 1,1’’-dimethyldispiro[indole-3,2’-[1,4]dithiane-3’,3’’-indole]-2,2’’(1H,1’’H)-dione (3a); A solution of 1c (178 mg, 0.75 mmol) in dry dichloromethane (10 ml) was added dropwise to a solution containing spiro-1,3-dithiolaneoxindole 2a (150 mg, 0.63 mmol) and rhodium(II) acetate dimer (2.9 mg, 0.56 mol%) in dry dichloromethane (20 ml) and then followed as described in general procedure to afford product 3a in 81% yield as a colourless solid; mp 264–266 °C; νmax(neat) 2921, 2851, 1699, 1606, 1489, 1372, 1342, 1255, 1088, 922, 752 cm−1; 1H NMR (CDCl3, 400 MHz) δ = 2.74-2.84 (m, 2H, SCH2), 3.16 (s, 6H, NCH3), 4.27-4.37 (m, 2H, SCH2), 6.55 (d, 2H, J = 7.6 Hz, ArH), 6.86 (td, 2H, J1 = 7.6 Hz, J2 = 0.8 Hz, ArH), 7.11 (td, 2H, J1 = 7.6 Hz, J2 = 1.2 Hz, ArH), 7.18 (dd, 2H, J1 = 7.2 Hz, J2 = 0.4 Hz, ArH); 13C NMR (CDCl3, 100 MHz) δ 25.50 (SCH2), 25.97 (NCH3), 45.90 (quat-C), 107.89 (=CH), 122.37 (=CH), 126.24 (quat-C), 129.74 (=CH), 142.88 (quat-C), 173.49 (C=O). HRMS (ESI) calcd for C20H18N2O2S2 (M+1)+: 383.0888 found 383.0883. Synthesis of 1-methyl-1’’-benzyldispiro[indole-3,2’-[1,4]dithiane-3’,3’’-indole]-2,2’’(1H,1’’H)-dione (3c); A solution of 1a (104 mg, 0.44 mmol) in dry dichloromethane (10 ml) was added dropwise to a solution containing spiro-1,3-dithiolaneoxindole 2a (100 mg, 0.40 mmol) and rhodium(II) acetate dimer (2.9 mg, 0.56 mol%) in dry dichloromethane (20 ml) and then followed as described in general procedure to afford product 3c in 60% yield as a colourless solid; mp 184–186 °C; νmax(neat) 2921, 2851, 1698, 1606, 1489, 1469, 1372, 1342, 1256, 1088, 752 cm−1; 1H NMR (CDCl3, 400 MHz) δ = 2.80-2.83 (m, 2H, SCH2), 3.19 (s, 3H, NCH3), 4.31-4.34 (m, 2H, SCH2), 4.91 (q, 2H, J = 15.6 Hz, NCH2), 6.50 (d, 1H, J = 8 Hz, ArH), 6.56 (d, 1H, J = 8 Hz, ArH), 6.68 (td, 1H, J1 = 7.6 Hz, J2 = 0.9 Hz, ArH), 6.84 (td, 1H, J1 = 7.6 Hz, J2 = 0.9 Hz, ArH), 7.03 (td, 1H, J1 = 7.7 Hz, J2 = 1.2 Hz, ArH), 7.08-7.13 (m, 2H, ArH), 7.20 (dd, 1H, J1 = 7.6 Hz, J2 = 0.8 Hz, ArH), 7.23-7.29 (m, 5H, ArH); 13C NMR (CDCl3, 100 MHz) δ 25.62 (SCH2), 25.68 (SCH2), 26.05 (NCH3), 43.69 (NCH2), 45.66 (quat-C), 45.88 (quat-C), 107.90 (=CH), 109.03 (=CH), 122.49 (=CH), 122.58 (=CH), 124.61 (=CH), 125.10 (=CH), 126.28 (quat-C), 126.35 (quat-C), 127.56 (=CH), 127.66 (=CH), 128.74 (=CH), 129.68 (=CH), 129.70 (=CH), 135.35 (quat-C), 142.20 (quat-C), 142.81 (quat-C), 173.39 (C=O), 173.52 (C=O); HRMS (ESI) calcd for C26H22N2O2S2 (M+1)+: 459.1201 found 459.1208. Synthesis of 1-benzyl-1’’-methyldispiro[indole-3,2’-[1,4]dithiepane-3’,3’’-indole]-2,2’’(1H,1’’H)-dione (3k); A solution of 1a (123 mg, 0.49 mmol) in dry dichloromethane (10 ml) was added dropwise to a solution containing spiro-1,3-dithianeoxindole 2f (100 mg, 0.41 mmol) and rhodium(II) acetate dimer (2.9 mg, 0.56 mol%) in dry dichloromethane (20 ml) and then followed as described in general procedure to afford product 3k in 67% yield as a colourless solid; mp 189–191 °C; νmax(neat) 2924, 2852, 1698, 1609, 1489, 1472, 1372, 1341, 1256, 1088, 750 cm−1; 1H NMR (CDCl3, 400 MHz) δ = 2.17-2.32 (m, 2H, SCH2), 2.51-2.58 (m, 2H, CCH2), 3.11 (s, 3H, NCH3), 4.79-4.92 (m, 4H, CH2), 6.42 (d, 1H, J = 7.6 Hz, ArH), 6.52 (d, 1H, J = 8.0 Hz, ArH), 6.65 (td, 1H, J1 = 8.0 Hz, J2 = 1.2 Hz, ArH), 6.79 (td, 1H, J1 = 7.6 Hz, J2 = 0.8 Hz, ArH), 6.95 (td, 1H, J1 = 7.6 Hz, J2 = 0.8 Hz, ArH), 7.04 (td, 1H, J1 = 7.6 Hz, J2 = 0.8 Hz, ArH), 7.08-7.10 (m, 2H, ArH), 7.17-7.19 (m, 4H, ArH), 7.26 (dd, 1H, J1 = 7.6 Hz, J2 = 0.4 Hz, ArH); 13C NMR (CDCl3, 100 MHz) δ 25.82 (SCH2), 26.00 (SCH2), 26.05 (NCH3), 31.42 (CCH2) 43.58 (NCH2), 52.70 (quat-C), 53.25 (quat-C), 108.03 (=CH), 109.14 (=CH), 122.60 (=CH), 122.75 (=CH), 125.10 (=CH), 125.65 (=CH), 126.10 (quat-C),127.34 (=CH), 127.55 (=CH), 128.69 (=CH), 129.28 (=CH), 135.30 (quat-C), 141.35 (quat-C), 141.92 (quat-C), 172.21 (C=O), 172.43 (C=O); HRMS (ESI) calcd for C27H24N2O2S2 (M+1)+: 473.1357 found 473.1355.
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