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J = 5.1 and J = 1.1 Hz, 1H), 7.03 (d, J = 3.1 Hz, 1H), 6.96 (dd, J = 5.1 and J = 3.6 Hz,
1H), 6.19 (dd, J = 5.6 and J = 2.1 Hz, 1H), 6.16 (t, J = 1.7, 1H); 13C NMR (100 MHz,
CDCl3): d (ppm) 172.1 (C@O), 154.4, 137.0, 127.7, 127.6, 127.5, 122.3, 79.7;
HRMS, Calculated [M]+ 167.0176, Measured [M]+ 167.0167.
(S)-(ꢀ)-6-(Furan-2-yl)-5,6-dihydro-2H-pyran-2-one, (S)-(ꢀ)-8a yield 65%; light
brown liquid; ½a D23:5
ꢂ
= ꢀ101.1 (c 1.00, CH2Cl2); mmax (cmꢀ1) 3122, 2911, 1727
(C@O); 1H NMR (400 MHz, CDCl3) d (ppm) 7.35 (dd, J = 1.8 and J = 0.8 Hz, 1H),
6.88 (ddd, J = 9.8, J = 5.7 and J = 2.8 Hz, 1H), 6.35 (d, J = 3.3 Hz, 1H), 6.30 (dd,
J = 3.3 and J = 1.8 Hz, 1H), 6.01 (ddd, J = 9.8, J = 2.5 and J = 1.1 Hz, 1H), 5.41 (dd,
J = 11.1 and J = 4.2 Hz, 1H), 2.90–2.52 (m, 2H); 13C NMR (100 MHz, CDCl3): d
(ppm) 161.9 (C@O), 149.5, 143.3, 141.9, 120.5, 109.5, 107.9, 71.2, 26.6; HRMS,
Calculated [M]+ 165.0473, Measured [M]+ 165.0558.
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_
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c
- and d-Lactones via RCM: 0.01 M CH2Cl2
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solution of first generation Grubbs catalyst [varied between 5 and 15 mol %]
was added to 0.01 M refluxing solution of acrylate ester (1 mmol) in CH2Cl2 by
slow addition under argon atmosphere. The reaction was stirred 80 min–24 h
at reflux and controlled by TLC. The solvent was evaporated in vacuum and the
purification of the crude product was done by column chromatography (silica
gel, EtOAc/hexane 1:3 for
c
-
and 1:2–1:4 for d-lactones). Representative
29. Zanella, A.; Berzuini, A.; Colombo, M. B.; Guffanti, A.; Lecchi, L.; Poli, F.;
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examples to
c
-
and d-lactones are given below, ‘respectively’. (S)-(ꢀ)-5-
(Thiophen-2-yl)furan-2(5H)-one, (S)-(ꢀ)-9b yield 60%; orange–brown thick
liquid; ½a 2D4:6
ꢂ
= ꢀ20.1 (c 1.00, CH2Cl2); mmax (cmꢀ1) 1754 (C@O), 1019, 823; 1H
NMR (400 MHz, CDCl3) d (ppm) 7.49 (dd, J = 5.6 and J = 1.7 Hz, 1H), 7.30 (dd,
31. Whitnall, M.; Howard, J.; Ponka, P.; Richardson, D. PNAS 2006, 103, 14901.