TBAHS-Catalyzed Synthesis of 2-Dihydroquinazolin-2-ylquinoline: An Efficient and Practical Synthesis of Naturally Occurring Alkaloids Luotonin A, B, and E

Lingaiah Nagarapu; Hanmant K. Gaikwad; Rajashaker Bantu

doi:10.1055/s-0032-1316537

Synlett, Inhaltsverzeichnis

Synlett 2012; 23(12): 1775-1778
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

Lingaiah Nagarapu*

Organic Chemistry Division-II, Indian Institute of Chemical Technology (CSIR), Tarnaka, Hyderabad 500607, India, Fax: +91(40)27193382 eMail: lnagarapuiict@yahoo.com eMail: nagarapu@iict.res.in

,

Hanmant K. Gaikwad

Organic Chemistry Division-II, Indian Institute of Chemical Technology (CSIR), Tarnaka, Hyderabad 500607, India, Fax: +91(40)27193382 eMail: lnagarapuiict@yahoo.com eMail: nagarapu@iict.res.in

,

Rajashaker Bantu

Organic Chemistry Division-II, Indian Institute of Chemical Technology (CSIR), Tarnaka, Hyderabad 500607, India, Fax: +91(40)27193382 eMail: lnagarapuiict@yahoo.com eMail: nagarapu@iict.res.in

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Abstract

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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) - Mitsunobu

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References and Notes

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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): ν_max = 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

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