References and Notes
-
1a
Attanasi OA.
De Crescentini L.
Filippone P.
Mantellini F.
Santeusanio S.
ARKIVOC
2002,
(xi):
274
-
1b
Attanasi OA.
De Crescentini L.
Favi G.
Filippone P.
Mantellini F.
Perrulli FR.
Santeusanio S.
Eur. J. Org. Chem.
2009,
3109
-
2a
Attanasi OA.
Caglioti L.
Org.
Prep. Proced. Int.
1986,
18:
299
-
2b
Schantl JG. In Houben-Weyl
Vol
E15:
Kropf H.
Schaumann E.
Thieme;
Stuttgart:
1990.
p.909-1100
-
3a
Zelenin KN.
Matveeva ZM.
Ermolaeva LYu.
Zh. Org.
Khim.
1970,
6:
723
-
3b
Zelenin KN.
Bezhan IP.
Matveeva ZM.
Khim. Geterosikl. Soedin.
1972,
579
-
3c
Zelenin KN.
Nikitin VA.
Anodina NM.
Khim. Geterosikl. Soedin.
1973,
124
-
4a
Boger DL.
Tetrahedron
1983,
39:
2869
-
4b
Gilchrist TL.
Stevens JA.
Parton B.
J. Chem. Soc., Perkin Trans. 1
1985,
1741
-
4c
Boger DL.
Chem. Rev.
1986,
86:
781
-
4d
Boger DL.
Weinreb SM.
Hetero Diels-Alder Methodology in
Organic Synthesis
Academic Press;
San Diego:
1987.
-
4e
Fringuelli F.
Taticchi A.
Dienes
in the Diels-Alder Reaction
Wiley Interscience;
New
York:
1990.
-
4f
South MS.
Jakuboski TL.
Westmeyer MD.
Dukesherer DR.
J.
Org. Chem.
1996,
61:
8921
-
4g
South MS.
J. Heterocycl. Chem.
1999,
36:
301
-
4h
Attanasi OA.
De Crescentini L.
Filippone P.
Fringuelli F.
Mantellini F.
Matteucci M.
Piermatti O.
Pizzo F.
Helv. Chim.
Acta
2001,
84:
513
-
4i
Fringuelli F.
Taticchi A.
The Diels-Alder
Reaction: Selected Practical Methods
John Wiley
and Sons;
New York:
2002.
- 5
D’Auria M.
Racioppi R.
Viggiani L.
Zanirato P.
Eur. J. Org. Chem.
2009,
932
- 8
Frisch MJ.
Trucks GW.
Schlegel HB.
Scuseria GE.
Robb MA.
Cheeseman JR.
Montgomery JA.
Vreven T.
Kudin KN.
Burant JC.
Millam JM.
Iyengar SS.
Tomasi J.
Barone V.
Mennucci B.
Cossi M.
Scalmani G.
Rega N.
Petersson GA.
Nakatsuji H.
Hada M.
Ehara M.
Toyota K.
Fukuda R.
Hasegawa J.
Ishida M.
Nakajima T.
Honda Y.
Kitao O.
Nakai H.
Klene M.
Li X.
Knox JE.
Hratchian HP.
Cross JB.
Adamo C.
Jaramillo J.
Gomperts R.
Stratmann RE.
Yazyev O.
Austin AJ.
Cammi R.
Pomelli C.
Ochterski JW.
Ayala PY.
Morokuma K.
Voth GA.
Salvador P.
Dannenberg JJ.
Zakrzewski VG.
Dapprich S.
Daniels AD.
Strain MC.
Farkas O.
Malick DK.
Rabuck AD.
Raghavachari K.
Foresman JB.
Ortiz JV.
Cui Q.
Baboul AG.
Clifford S.
Cioslowski J.
Stefanov BB.
Liu G.
Liashenko A.
Piskorz P.
Komaromi I.
Martin RL.
Fox DJ.
Keith T.
Al-Laham MA.
Peng CY.
Nanayakkara A.
Challacombe M.
Gill PMW.
Johnson B.
Chen W.
Wong MW.
Gonzalez C.
Pople JA.
Gaussian 03, Revision
A.1
Gaussian Inc.;
Pittsburgh:
2003.
6
Synthesis of Compound
3a
DD 1a (370 mg; 2 mmol)
was added under vigorous stirring to a solution of methyl crotonate
(2a, 2.0 g; 20 mmol) in MeCN (40 mL). The
reaction was heated to reflux for 48 h, and then the solvent was
evaporated under reduced pressure to afford the crude mixture, which
was chromatographed on silica gel (EtOAc-PE, 1:1
to 7:3) to give pure THP 3a (370 mg, 65% yield).
7 Compound 3a: ¹H
NMR (500 MHz, CDCl3): δ = 6.40-6.00 (2
H, br s), 5.00 (1 H, q, J = 6.8
Hz), 4.17 (2 H, m), 3.65 (3 H, s), 3.51 (1 H, s), 3.42 (1 H, s),
2.14 (3 H, s), 1.26 (3 H, t, J = 7.2
Hz), 1.04 (3 H, d, J = 6.8
Hz) ppm. ¹³C NMR (125 MHz, CDCl3): δ = 169.49,
167.29, 153.79, 139.07, 59.58, 50.46, 41.53, 40.98, 38.56, 22.02,
14.42, 11.61 ppm. MS:
m/z (%)
285 (23), 239 (80), 226 (7), 211 (10), 197 (10), 196 (38), 184 (7),
183 (28), 181 (13), 169 (18), 168 (10), 167 (48), 155 (8), 154 (23),
153 (100), 141 (13), 139 (8), 137 (27), 128 (22), 109 (32), 96 (27),
95 (35). Anal. Calcd (%) for C12H19N3O5:
C, 50.52; H, 6.71; N, 14.73. Found: C, 50.55; H, 6.68; N, 14.75.
Compound 3b: ¹H NMR (500 MHz,
CDCl3): δ = 6.40-5.80 (2 H,
br s), 5.01 (1 H, q, J = 6.8
Hz), 3.70 (3 H, s), 3.64 (3 H, s), 3.57 (1 H, s), 3.41 (1 H, s),
2.56 (1 H, dq, J
1 = J
2 = 7.6 Hz),
2.37 (1 H, dq, J
1 = J
2 = 7.6
Hz), 1.11 (3 H, t, J = 7.6 Hz),
1.03 (3 H, d, J = 6.8
Hz) ppm.¹³C NMR (125 MHz, CDCl3): δ = 171.92,
170.63, 156.55, 145.15, 52.98, 52.89, 44,40, 43.53, 39.55, 30.50,
17.12, 10.68 ppm. MS: m/z (%) = 285
(19), 254 (17), 253 (52), 226 (10), 211 (11), 210 (25), 183 (29),
181 (17), 168 (18), 167 (100), 151 (13), 142 (10), 128 (18), 123
(16), 113 (10), 110 (11), 109 (21), 96 (11). Anal. Calcd (%)
for C11H17N3O5: C, 48.70;
H, 6.32; N, 15.49. Found: C, 48.73; H, 6.36; N, 15.46.
Compound 3c: ¹H NMR (500 MHz,
CDCl3): δ = 8.44 (1 H, s), 7.41 (2
H, m), 7.20 (2 H, m), 6.94 (1 H, m), 5.07 (1 H, q, J = 7.5
Hz), 3.70 (3 H, s), 3.62 (3 H, s), 3.52 (1 H, s), 3.44 (1 H, s),
2.19 (3 H, s), 1.05 (3 H, d, J = 7.5
Hz) ppm. ¹³C NMR (125 MHz, CDCl3): δ = 172.02,
170.37, 152.19, 141.57, 138.62, 129.11, 123.18, 119.34, 53.16, 53.04,
44.26, 43.67, 41.16, 24.68, 17.04 ppm. MS: m/z (%) = 348
(8), 347 (44), 316 (9), 315 (40), 197 (21), 196 (70), 170 (8), 169
(59), 167 (13), 155 (14), 154 (24), 153 (100), 138 (18), 129 (38),
109 (26), 96 (24), 95 (28), 77 (12). Anal. Calcd (%) for C17H21N3O5:
C, 58.78; H, 6.09; N, 12.10. Found: C, 58.72; H, 6.12; N, 12.05.
Compound 3d: ¹H NMR (500 MHz,
CDCl3): δ = 6.50-6.00 (2 H,
br s), 4.71 (1 H, d, J = 1.0
Hz), 4.19 (2 H, m), 3.74 (3 H, s), 3.67 (1 H, s), 3.45 (1 H, dd, J
1 = J
2 = 1.0
Hz), 2.75 (1 H, d, J = 1.0
Hz), 2.12 (3 H, s), 1.29 (3 H, t, J = 7.0
Hz) ppm. ¹³C NMR (125 MHz, CDCl3): δ = 170.87,
168.54, 156.71, 139.75, 62.06, 52.50, 43.88, 39.26, 37.16, 23.53,
14.29 ppm. MS: m/z (%) = 271
(10), 226 (8), 225 (36), 212 (8), 183 (9), 182 (24), 170 (9), 169
(92), 167 (9), 155 (14), 154 (16), 153 (28), 141 (16), 140 (8),
139 (45), 128 (30), 123 (23), 114 (11), 97 (7), 96 (32), 95 (100),
82 (28), 68 (10), 67 (8), 59 (8), 55 (24), 54 (12), 53 (9), 44 (26).
Anal. Calcd (%) for C11H17N3O5:
C, 48.70; H, 6.32; N, 15.49. Found: C, 48.65; H, 6.35; N, 15.52.
Compound 3e: ¹H NMR (500 MHz,
CDCl3): δ = 6.20-5.10 (2 H,
br s), 4.10 (2 H, q, J = 7.0
Hz), 3.63 (3 H, s), 3.10 (1 H, dd, J
1 = 12.0
Hz, J
2 = 5.6
Hz), 2.31 (1 H, s), 1.95 (1 H, dd, J
1 = 12.0
Hz, J
2 = 5.6
Hz), 1.91 (3 H, s), 1.39 (3 H, s), 1.22 (3 H, t, J = 7.0
Hz) ppm. ¹³C NMR (125 MHz, CDCl3): δ = 173.26,
170.92, 156.40, 140.74, 61.90, 60.47, 56.82, 56.52, 40.26, 32.43,
20.36, 14.25 ppm. MS: m/z (%) = 285
(4), 242 (6), 184 (12), 183 (100), 142 (12), 109 (28), 96 (10).
Anal. Calcd (%) for C12H19N3O5:
C, 50.52; H, 6.71; N, 14.73. Found: C, 50.55; H, 6.68; N, 14.77.
Compound 3f: ¹H NMR (500 MHz,
CDCl3): δ = 9.40 (1 H, s), 7.07 (1
H, dq, J
1 = 14.0
Hz, J
2 = 7.0
Hz), 6.20-6.00 (1 H, br s), 5.91 (1 H, dd, J
1 = J
2 = 14.0
Hz), 5.7 (1 H, br s), 5.57 (1 H, d, J = 14.0
Hz), 4.21 (2 H, q, J = 7.0
Hz), 1.94 (3 H, s), 1.89 (3 H, d, J = 7.0
Hz), 1.26 (3 H, t, J = 7.0
Hz) ppm. ¹³C NMR (125 MHz, CDCl3): δ = 176.00,
167.35, 165.29, 158.80, 147.39, 143.35, 121.55, 62.21, 18.40, 14.33,
13.00 ppm. MS: m/z (%) = 255
(29), 227 (12), 226 (100), 209 (50), 184 (10), 183 (67), 181 (10),
167 (27), 166 (30), 151 (47), 142 (20), 139 (30), 137 (26), 125
(10), 124 (20), 123 (26), 111 (32), 110 (10), 109 (23), 98 (22),
97 (13), 96 (33), 95 (57), 94 (11), 83 (24), 70 (14), 69 (72), 68
(13). Anal. Calcd (%) for C11H17N3O4:
C, 51.76; H, 6.71; N, 16.46. Found: C, 51.80; H, 6.65; N, 16.42.
Compounds 3g and 3h: ¹H
NMR (500 MHz, CDCl3): δ = 9.11 (s,
1 H), 7.15 (3 H, m), 7.01 (2 H, m), 6.60-6.10 (0.33 H,
br s), 6.07 (0.66 H, s), 5.60-5.00 (0.66 H, br s), 4.91
(0.33 H, s), 4.05 (2 H, m), 3.82 (0.66 H, s), 3.67 (1.98 H, s),
3.64 (0.33 H, s), 3.58 (0.99 H, s), 3.38 (0.66 H, s), 3.09 (0.33
H, s), 2.08 (1.98 H, s), 2.05 (0.99 H, s), 1.13 (3 H, t, J = 7.0 Hz) ppm. ¹³C
NMR (125 MHz, CDCl3): δ = 171.57, 170.36, 169.54,
168.38, 157.08, 156.58, 142.70, 141.43, 140.87, 137.23, 129.22,
128.53, 127.82, 127.72, 126.97, 126.18, 62.16, 61.57, 53.65, 53.17,
46.22, 44.07, 40.85, 38.67, 24.78, 24.20, 14.16, 13.72. MS (3g): m/z (%) = 347
(36), 302 (21), 301 (100), 226 (17), 258 (13), 243 (20), 242 (14),
231 (30), 230 (28), 229 (73), 217 (18), 216 (10), 215 (38), 202 (24),
200(29), 199 (43), 190 (21), 189 (35), 188 (13), 172 (16), 171 (70),
167 (13), 159 (13), 158 (47), 157 (13), 156 (16), 155 (17), 154
(32), 153 (26), 146 (19), 143 (10), 142 (12), 141 (17), 139 (10),
131 (38), 130 (42), 129 (12), 128 (48), 127 (10), 115 (23), 113
(11), 106 (20), 105 (19), 104 (73), 103 (26), 96 (27), 95 (36),
91 (14), 78 (10), 77 (39), 68 (12). MS (3h): m/z (%) = 347
(13), 304 (11), 288 (38), 246 (16), 245 (100), 204 (23), 199 (10),
172 (15), 171 (61), 158 (23), 131 (18), 130 (20), 103 (15), 95 (19).
Anal. Calcd (%) for C17H21N3O5:
C, 58.78; H, 6.09; N, 12.10. Found: C, 58.70; H, 6.15; N, 12.16.