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Synlett 2012; 23(12): 1775-1778
DOI: 10.1055/s-0032-1316537
DOI: 10.1055/s-0032-1316537
letter
TBAHS-Catalyzed Synthesis of 2-Dihydroquinazolin-2-ylquinoline: An Efficient and Practical Synthesis of Naturally Occurring Alkaloids Luotonin A, B, and E
Further Information
Publication History
Received: 04 April 2012
Accepted after revision: 19 May 2012
Publication Date:
29 June 2012 (online)
Abstract
A synthesis of 2-dihydroquinazolin-2-ylquinoline using a phase-transfer catalyst (TBAHS) in semi-aqueous phase, followed by Mitsunobu cyclization as key steps for an efficient and practical synthesis of naturally occurring alkaloids luotonin A, B, and E starting from o-nitrobenzaldehyde is reported. The new approach presents the advantage of a shorter route with high overall yield (57%, 45%, and 37%, respectively) and ease of operation.
Key words
luotonins - 2-dihydroquinazolin-2-ylquinoline - tetrabutylammonium hydrogen sulfate (TBAHS) - MitsunobuSupporting Information
- for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
- Supporting Information
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11
General Procedure for the Synthesis of 2-Dihydroquinazolin-2-ylquinoline (6a)
Aldehyde 4 (4 g, 17.46 mmol), o-aminobenzamide (2.38 g, 17.46 mmol), and TBAHS (1.8 g, 5.42 mmol) were added to MeOH–H2O (5 mL, 1:1) at r.t. The resulting mixture was heated at 80 °C for 0.5 h, and completion of the reaction was monitored by TLC (EtOAc–hexane = 7:3). After completion of the reaction, reaction mixture was allowed to cool, diluted with H2O, and extracted with EtOAc. The organic layer were combined and washed thoroughly with sat. aq NaCl, dried over Na2SO4. The organic layer was evaporated under vacuum, the residue obtained was subjected to chroma-tography on silica gel. The desired 2-dihydroquinazolin-2-ylquinoline (6a) was obtained in 95% yield; mp 194–196 °C. IR (KBr): νmax = 3327, 3247, 2924, 1710, 1653, 1611, 1511, 1137, 1018, 776, 747 cm–1. 1H NMR (300 MHz, DMSO-d 6): δ = 1.48 (t, J = 7.17 Hz, 3 H, CH3), 4.48 (q, J = 7.17 Hz, 2 H, CH2), 6.47 (br s, 1 H, NH), 6.53 (s, 1 H, CH), 6.66 (t, J = 8.28 Hz, 2 H, ArH), 7.11 (t, J = 7.65 Hz, 1 H, ArH), 7.60 (t, J = 7.36 Hz, 1 H, ArH), 7.65–7.83 (m, 3 H, ArH), 7.90–8.03 (m, 2 H, ArH), 8.89 (s, 1 H, NH). 13C NMR (75 MHz, DMSO-d 6): δ = 14.19, 61.38, 71.79, 120.76, 124.81, 126.52, 126.98, 127.18, 127.69, 127.87, 129.07, 130.16 (2 C), 130.67, 134.18 (2 C), 138.03, 146.84, 158.80, 165.37. HRMS (ESI+): m/z calcd for C20H17N3O3 [M + Na]+: 370.1167; found: 370.1173