Regioselective Synthesis of Highly Functionalized Biaryls through Carbanion Induced Ring Transformation of 2H-Pyran-2-ones [1]

Abstract

An expedient synthesis of highly functionalized unsymmetrical biaryls 3 of which one of the two phenyl rings substituted with carbomethoxy, amino and nitrile functionalities is described and illustrated by carbanion induced ring transformation of 6-aryl-3-carbomethoxy-4-methylsulfanyl-2H-pyran-2-one 1 using malononitrile 2 as a source of carbanion in moderate yield.

biaryls - 2H-pyran-2-one - malononitrile - biaryls - carb­anion - ring transformation

References

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18

General Procedure for the Synthesis of 3a: A mixture of 6-aryl-3-carbomethoxy-4-methylsulfanyl-2H-pyran -2-one 1(0.28 g, 1 mmol), malononitrile (0.07 g, 1 mmol) and powdered KOH (0.06 g, 1 mmol) in dry DMF (12 mL) was stirred at r.t. for 30 h. At the end reaction mixture was poured into ice water with vigorous stirring and finally neutralized with 10% HCl. The solid thus obtained was filtered and purified on a silica gel column using chloroform as eluent; white solid, yield 0.12 g (40.26%), mp 170 °C. IR (KBr): ν_max = 3444, 2209 (medium and sharp), 1672 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.45 (s, 3 H, SCH₃), 3.98 (s, 3 H, OCH₃), 6.41 (brs, 2 H, NH₂), 6.55 (s, 1 H, ArH), 7.47-7.54 (m, 5 H, ArH). MS (EI): m/z = 298 (M⁺), 266. Anal. Calcd for C₁₆H₁₄N₂O₂S: C, 64.41; H, 4.73; N, 9.39. Found: C, 64.54; H, 4.77; N, 9.44. 3d: White solid; mp 185 °C. IR (KBr): ν_max = 3422, 2208 (medium and sharp), 1680 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.44 (s, 3 H, SCH₃), 3.98 (s, 3 H, OCH₃), 6.42 (brs, 2 H, NH₂) 6.50 (s, 1 H, ArH), 7.47 (s, 4 H, ArH). ¹³C NMR (200 MHz, CDCl₃): δ = 17.06, 52.26, 93.23, 109.76, 114.31, 117.31, 129.43, 130.12, 135.99, 136.9, 147.54, 151.88, 153.07, 164.49. MS (EI): m/z = 332, 300, 176. Anal. Calcd for C₁₆H₁₃ClN₂O₂S: C, 57.74; H, 3.94; N, 8.41. Found: C, 57.83; H, 3.98; N, 8.52.