A New Method for Introducing a Carbalkoxymethyl Group Into Pyridinocyclo-α-alkanones

References

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• The cis and trans fused tricyclic lactones 7 and 8 (1:1) were obtained. Structural assignments were based on H1, C13, COSY and XH CORR NMR data. 7:Anal. Calcd for C13H15NO3.HCl C, 57.89; H, 5.98; N, 5.19; Found C, 57.84; H, 5.99; N, 5.03 (the hydrochloride salt was used for elemental analysis).1H NMR (DMSO-d6/TMS; 200 MHz) δ 0.8–0.11 (m, 1H, Ha), 1.4–1.7 (m, 2H, Hb and one of Hc protons), 1.7–2.0 (m, 1H, one of Hc protons), 2.35 (dd, J = 5, 17.6 Hz, one of Hh protons), 2.6–2.9 (m, 2H, Hf and one of Hd protons), 2.9–3.3 (m, 2H, one of Hd protons and one of Hh protons), 3.0 (s, 3H, OCH3), 7.35 (dd, 8.3, 5.5 Hz, 1H, NCHCH), 7.85 (dd, 8.3, 1.1 Hz, 1H, NCHCHCH), 8.55 (dd, 5.5, 1.1 Hz, 1H, NCH); IR (neat): 1770 cm−1. 8: Anal. Calcd for C13H15NO3 C, 66.74; H, 6.48; H 6.01; Found C, 66.96; H, 6.45; N, 5.97. 1H NMR (CDCl3/TMS; 500 MHz) δ 1.58 (qm, 26.6, 13.9 Hz, 1H, one of Hc protons), 1.94 (dq, 13.9, 6.9, 3.5 Hz, 1H, Ha), 2.03–2.11 (m, 1H, one of Hc protons), 2.20 (qd, 26.6, 13.9, 3.5 Hz, 1H, Hb), 2.41–2.48 (m, 1H, Hf), 2.55–2.67 (m, 2H, Hh), 3.04 (dd, 14.1, 7.0 Hz, 1H, one of Hd protons) 3.11 (s, 3H, OCH3), 3.30 (td, 14.1, 1.7 Hz, 1H, one of Hd protons), 7.19 (dd, 8.3, 5.5 Hz, 1H), 7.94 (dd, 8.3, 1.1 Hz, 1H), 8.46 (dd, 5.5, 1.1 Hz, 1H). IR(Neat) 1785 cm−1
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• Various oxidations such as K2S2O8/AgNO3, AgNO3/KOH, pyridinium dichromate, calcium hypochlorite in acetonitrile, and sodium periodate were used
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