References
<A NAME="RD03205ST-1A">1a</A>
Jones TH.
Blum MS. In
Alkaloids: Chemical and Biological Perspectives
Vol. 1:
Pelletier SW.
Wiley;
New York:
1985.
p.33-84
<A NAME="RD03205ST-1B">1b</A>
Jones TH.
Blum MS. In Alkaloids: Chemical and Biological Perspectives
Vol. 3:
Pelletier SW.
Wiley;
New York:
1985.
p.1-90
<A NAME="RD03205ST-1C">1c</A>
Daly JW.
J. Nat. Prod.
1998,
61:
162
<A NAME="RD03205ST-1D">1d</A>
Plunkett AO.
Nat. Prod. Rep.
1994,
11:
s581
<A NAME="RD03205ST-1E">1e</A>
Balasubramaniam M.
Keay JG. In
Comprehensive Heterocyclic Chemistry II
Katritzky AR.
Rees CW.
Scriven EFV.
Pergamon Press;
New York:
1996.
Chap. 5.
p.245
<A NAME="RD03205ST-1F">1f</A>
Rubiralta M.
Giralt E.
Diez A. In
Piperidine: Structure, Preparation, Reactivity and Synthetic Applications of Piperidine and its
Derivatives
Elsevier;
Amsterdam:
1991.
<A NAME="RD03205ST-2">2</A>
Paulvannan K.
Chen T.
J. Org. Chem.
2000,
65:
6160 ; and references therein
<A NAME="RD03205ST-3">3</A> Review:
Stille JR.
Barta NS.
Stud. Nat. Prod. Chem.
1996,
18:
315
<A NAME="RD03205ST-4A">4a</A>
Paulvannan K.
Stille JR.
J. Org. Chem.
1992,
57:
5319
<A NAME="RD03205ST-4B">4b</A>
Paulvannan K.
Schwarz JB.
Stille JR.
Tetrahedron Lett.
1993,
34:
215
<A NAME="RD03205ST-4C">4c</A>
Barta NS.
Brode A.
Stille JR.
J. Am. Chem. Soc.
1994,
116:
6201
<A NAME="RD03205ST-4D">4d</A>
Paulvannan K.
Stille JR.
J. Org. Chem.
1994,
59:
1613
<A NAME="RD03205ST-5A">5a</A>
Benovsky P.
Stille JR.
Tetrahedron Lett.
1997,
38:
8475
<A NAME="RD03205ST-5B">5b</A>
Agami C.
Dechoux L.
Menard C.
Hebbe S.
J. Org. Chem.
2002,
67:
7573
<A NAME="RD03205ST-5C">5c</A>
Shen W.
Coburn CA.
Bornmann WG.
Danishefsky SJ.
J. Org. Chem.
1993,
58:
611
<A NAME="RD03205ST-6A">6a</A>
Cook GR.
Beholz LG.
Stille JR.
Tetrahedron Lett.
1994,
35:
1669
<A NAME="RD03205ST-6B">6b</A>
Cook GR.
Beholz LG.
Stille JR.
J. Org. Chem.
1994,
59:
3575
<A NAME="RD03205ST-7A">7a</A>
Paulvannan K.
Stille JR.
Tetrahedron Lett.
1993,
34:
8197
<A NAME="RD03205ST-7B">7b</A>
Beholz LG.
Benovsky P.
Ward DL.
Barta NS.
Stille JR.
J. Org. Chem.
1997,
62:
1033
<A NAME="RD03205ST-7C">7c</A>
Benovsky P.
Stephenson GA.
Stille JR.
J. Am. Chem. Soc.
1998,
120:
2493
<A NAME="RD03205ST-7D">7d</A>
Agami C.
Hamon L.
Kadouri-Puchot C.
LeGuen V.
J. Org. Chem.
1996,
61:
5736
<A NAME="RD03205ST-8">8</A>
Murphy JP.
Hadden M.
Stevenson PJ.
Tetrahedron
1997,
53:
11827
<A NAME="RD03205ST-9">9</A>
Ambroise L.
Desmaele D.
d’Angelo J.
Tetrahedron Lett.
1994,
35:
9705
Reviews:
<A NAME="RD03205ST-10A">10a</A>
Junjappa H.
Ila H.
Asokan CV.
Tetrahedron
1990,
46:
5423
<A NAME="RD03205ST-10B">10b</A>
Tominaga Y.
J. Heterocycl. Chem.
1989,
26:
1167
<A NAME="RD03205ST-10C">10c</A>
Ila H.
Junjappa H.
Mohanta PK.
Progress in Heterocyclic Chemistry
Vol. 13:
Gribble GW.
Gilchrist TL.
Pergamon;
New York:
2001.
Chap. 1.
p.1
<A NAME="RD03205ST-11A">11a</A>
Mahata PK.
Venkatesh C.
Syam Kumar UK.
Ila H.
Junjappa H.
J. Org. Chem.
2003,
68:
3996
<A NAME="RD03205ST-11B">11b</A>
Barun O.
Mohanta PK.
Ila H.
Junjappa H.
Synlett
2000,
653
<A NAME="RD03205ST-11C">11c</A>
Barun O.
Ila H.
Junjappa H.
Singh OM.
J. Org. Chem.
2000,
65:
1583
<A NAME="RD03205ST-11D">11d</A>
Syamkumar UK.
Ila H.
Junjappa H.
Org. Lett.
2001,
3:
4193
<A NAME="RD03205ST-11E">11e</A>
Barun O.
Chakrabarti S.
Ila H.
Junjappa H.
J. Org. Chem.
2001,
66:
4457
<A NAME="RD03205ST-12A">12a</A>
Aggarwal V.
Ila H.
Junjappa H.
Synthesis
1983,
147
<A NAME="RD03205ST-12B">12b</A>
Aggarwal V.
Ila H.
Junjappa H.
Synthesis
1982,
65
<A NAME="RD03205ST-12C">12c</A>
Purkayastha ML.
Chandrasekharan M.
Ila H.
Junjappa H.
Indian J. Chem., Sect. B: Org. Chem. Incl. Med. Chem.
1991,
30:
646
<A NAME="RD03205ST-12D">12d</A>
Chakrasali RT.
Ila H.
Junjappa H.
Synthesis
1988,
87
<A NAME="RD03205ST-12E">12e</A>
Gupta AK.
Ila H.
Junjappa H.
Synthesis
1988,
284
<A NAME="RD03205ST-12F">12f</A>
Gupta AK.
Reddy KR.
Ila H.
Junjappa H.
J. Chem. Soc., Perkin Trans. 1
1995,
1725
Aza-annulation of enaminones/esters with itaconic anhydride:
<A NAME="RD03205ST-13A">13a</A>
Fang FG.
Danishefsky SJ.
Tetrahedron Lett.
1989,
28:
3621
<A NAME="RD03205ST-13B">13b</A>
Hadden M.
Nieuwenhuyzen .
Potts D.
Stevenson PJ.
J. Chem. Soc., Perkin Trans. 1
1994,
3432
Aza-annulation of enaminones/esters with maleic anhydride derivatives:
<A NAME="RD03205ST-14A">14a</A>
Nagasaka T.
Inque H.
Ichimura M.
Hamaguchi F.
Synthesis
1982,
848
<A NAME="RD03205ST-14B">14b</A>
Robson JH.
Marcus E.
Chem. Ind. (London, UK)
1970,
1022
<A NAME="RD03205ST-14C">14c</A>
von Bobeneck H.
Brunner E.
Bunke H.
Metzner G.
Schmidt R.
Weil E.
Sonnenbichler J.
Liebigs. Ann. Chem.
1981,
410
<A NAME="RD03205ST-15A">15a</A>
Cave C.
Gassama A.
Mahuteau J.
d’Angelo J.
Riche C.
Tetrahedron Lett.
1997,
38:
4773
<A NAME="RD03205ST-15B">15b</A>
d’Angelo J.
Cave C.
desmaele D.
Isr. J. Chem.
1997,
37:
81
<A NAME="RD03205ST-16A">16a</A>
Gompper R.
Schaefer FC.
Chem. Ber.
1967,
100:
591
<A NAME="RD03205ST-16B">16b</A>
Rudorf WD.
Schierhorn A.
Augustin M.
Tetrahedron
1979,
35:
551
<A NAME="RD03205ST-17">17</A>
General procedure for the aza-annulation of acyclic and cyclic α-oxo- and α-nitro
N,S- and N,N-ketene acetals with itaconic anhydride: A solution of the appropriate
N,S- or N,N-ketene acetal (1 mmol) and itaconic anhydride (0.12 g, 1.1 mmol) in anhyd
acetonitrile (30 mL) was refluxed under a nitrogen atmosphere for 8-10 h (monitored
by TLC). The reaction mixture was concentrated under reduced pressure and the residue
was subjected to column chromatography over silica gel using hexane-EtOAc (4:1) (4a-f, 6a,b, 8a-f, 12, 14) as eluent to give pure compounds.
4a. Yield 70%; white solid (CHCl3-hexane); mp 138-140 °C; R
f
0.5 (EtOAc); IR (KBr): 3032, 2924, 1698, 1668, 1629, 1596 cm-1; 1H NMR (400 MHz, CDCl3): δ = 1.99 (s, 3 H, SCH3), 2.56 (dd, J = 6.6 Hz, 16.8 Hz, 1 H, CHHCO2H), 2.57-2.60 (m, 2 H, =CCH
2CH),2.94 (dd, J = 6.6 Hz, 16.8 Hz, 1 H, CHHCO2H), 3.17-3.23 (m, 1 H, CHCH2CO2H), 4.91 (d, J = 15.0 Hz, 1 H, NCHHPh), 5.41 (d, J = 15.0 Hz, 1 H, NCHHPh), 7.25-7.35 (m, 5 H, ArH), 7.39-7.45 (m, 2 H, ArH), 7.54 (t, J = 7.4 Hz, 1 H, ArH), 7.72 (d, J = 7.6 Hz, 2 H, ArH), 8.91 (br s, 1 H, CO2H); 13C NMR (100 MHz, CDCl3): δ = 19.0, 29.14, 34.26, 37.22, 46.17, 127.32, 127.43, 128.56, 128.63, 129.05, 133.29,
137.12, 137.58, 137.68, 171.46, 176.98, 195.16; FABMS: m/z (%) = 396 (MH+, 100); Anal. Calcd for C22H21NO4S (395.47): C, 66.82; H, 5.35; N, 3.54. Found: C, 66.65; H, 5.40; N, 3.48.
6a. Yield 80%; yellow solid (CHCl3-hexane); mp 152-153 °C; R
f
0.20 (hexane-EtOAc 7:3); IR (KBr): 3438, 2962, 2365, 1714, 1567 cm-1; 1H NMR (400 MHz, DMSO-d
6
): δ = 2.37 (s, 3 H, SCH3), 2.41-2.54 (m, 2 H, CH
2CO2H), 2.68 (dd, J = 5.6 Hz, 16.8 Hz, 1 H, =CCHH), 2.86-2.88 (m, 2 H, CH2Ph), 3.06-3.12 (m, 1 H, CHCH2CO2H), 3.20 (dd, J = 5.9 Hz, 16.1 Hz, 1 H, CHHCO2H), 3.91-3.98 (m, 1 H, NCHH), 4.37-4.42 (m, 1 H, NCHH), 7.21-7.29 (m, 5 H, ArH), 12.40 (br s, 1 H, CO2H); 13C NMR (100 MHz, DMSO-d
6
): d = 17.77, 26.46, 33.41, 34.23, 36.31, 47.96, 126.60, 128.33, 128.95, 137.49, 137.84,
150.07, 171.30, 172.71; FABMS: m/z (%) = 351 (MH+, 100); Anal. Calcd for C16H18N2O5S (350.39): C, 54.84; H, 5.18; N, 7.99. Found: C, 54.81; H, 5.22; N, 7.94.
8b. Yield 86%; white solid (CHCl3-hexane); mp 203-204 °C; R
f
0.49 (EtOAc); IR (KBr): 1732, 1691, 1637, 1504 cm-1; 1H NMR (400 MHz, DMSO-d
6
): d = 2.39 (dd, J = 7.0 Hz, 16.9 Hz, 1 H, CHHCO2H), 2.55-2.78 (m, 3 H, =CCH2 and CHHCO2H), 2.83-2.91 (m, 1 H, CHCH2CO2H), 3.76-3.86 (m, 3 H, HNCH
2 and NCHH), 3.94-4.02 (m, 1 H, NCHH), 7.35-7.42 (m, 5 H, ArH), 9.50 (br s, 1 H, CO2H), 12.50 (br s, 1 H, NH); 13C NMR (100 MHz, DMSO-d
6
): d = 27.71, 33.79, 38.36, 41.60, 42.50, 83.99, 126.48, 127.49, 128.71, 141.0, 156.19,
169.82, 172.73, 189.38; FABMS: m/z (%) = 301 (MH+, 100); Anal. Calcd for C16H16N2O4 (300.31): C, 63.99; H, 5.37; N, 9.33. Found: C, 63.76; H, 5.46; N, 9.17.
8d. Yield 57%; white solid (CHCl3-hexane); mp 196-197 °C; R
f
0.52 (EtOAc); IR (KBr): 2975, 1732, 1618, 1501 cm-1; 1H NMR (400 MHz, DMSO-d
6
): d = 2.52 (dd, J = 6.4 Hz, 17.0 Hz, 1 H, CHHCO2H), 2.64-2.75 (m, 2 H, =CCH2), 3.01-3.07 (dd, J = 6.4 Hz, 17.0 Hz, 1 H, CHHCO2H), 3.09-3.19 (m, 1 H, CHCH2CO2H), 3.24 (t, J = 7.7 Hz, 2 H, SCH2), 3.90-3.96 (m, 1 H, NCHH), 4.27-4.33 (m, 1 H, NCHH), 12.41 (br s, 1 H, CO2H); 13C NMR (100 MHz, DMSO-d
6
): d = 26.57, 28.56, 33.78, 36.32, 49.21, 121.83, 157.89, 168.67, 172.56; FABMS: (m/z) = 258 (MH+, 45); Anal. Calcd for C9H10N2O5S (258.25): C, 41.86; H, 3.90; N, 10.85. Found: C, 41.65; H, 4.02; N, 10.68.
12. Yield 90%; white crystalline solid (CHCl3-hexane); mp 172-174 °C; R
f
0.55 (EtOAc); IR (KBr): 3059, 2982, 1712, 1667, 1598 cm-1; 1H NMR (400 MHz, CDCl3): d = 1.90 (d, J = 7.1 Hz, 3 H, CH
3CH), 1.94 (s, 3 H, SCH3), 2.49-2.67 (m, 3 H, =CCH
2CH and CHHCO2H), 2.92 (dd, J = 6.4 Hz, 17.1 Hz, 1 H, CHHCO2H), 3.11-3.16 (m, 1 H, CH2CHCH2CO2H), 5.96-6.06 (m, 1 H, CHCH3), 7.21-7.57 (m, 8 H, ArH), 7.69-7.71 (m, 2 H, ArH), 10.20 (br s, 1 H, CO2H); 13C NMR (100 MHz, CDCl3): d = 7.77, 20.02, 29.39, 34.24, 37.93, 53.55, 126.76, 126.98, 128.21, 128.55, 129.17,
130.83, 133.31, 136.53, 137.92, 140.55, 171.41, 176.96, 195.05; FABMS: m/z (%) = 410 (M + 1, 50); Anal. Calcd for C23H23NO4S (409.50): C, 67.46; H, 5.66; N, 3.42. Found: C, 67.29; H, 5.80; N, 3.31.
14. Yield 71% (0.35 g); white solid (CHCl3-hexane); mp 136-137 °C; R
f
0.55 (EtOAc); IR (KBr): 2933, 2546, 1693, 1549, 1418 cm-1; 1H NMR (400 MHz, DMSO-d
6
): δ = 2.50 (dd, J = 7.6 Hz, 17.1 Hz, 1 H, =CCHH), 2.59 (dd, J = 7.6 Hz, 17.1 Hz, 1 H, =CCHH), 2.66 (s, 3 H, SCH3), 2.88 (dd, J = 6.8 Hz, 15.6 Hz, 1 H, CHHCO2H), 2.98 (dd, J = 6.8 Hz, 15.6 Hz, 1 H, CHHCO2H), 3.06-3.13 (m, 1 H, CHCH2CO2H), 3.35 (br s, 1 H, NH), 12.45 (br s, 1 H, CO2H); 13C NMR (100 MHz, DMSO-d
6
): d = 14.42, 24.30, 34.84, 38.51, 151.05, 153.13, 172.67, 174.16; FABMS: m/z (%) = 247 (M + 1+, 70); Anal. Calcd for C8H10N2O5S (246.24): C, 39.02; H, 4.09; N, 11.38. Found: C, 39.19; H, 3.97; N, 11.52.
<A NAME="RD03205ST-18">18</A>
Chakrabarti S.
Srivastava MC.
Ila H.
Junjappa H.
Synlett
2003,
2369
<A NAME="RD03205ST-19A">19a</A>
Rajappa S.
Tetrahedron
1981,
37:
1453
<A NAME="RD03205ST-19B">19b</A>
Rajappa S.
Tetrahedron
1999,
55:
7065
<A NAME="RD03205ST-20">20</A> X-ray crystallographic data of structure 12 has been deposited at the Cambridge Crystallographic Data Centre and has been allocated
the deposition number CCDC 268032
<A NAME="RD03205ST-21A">21a</A>
Dieter RK.
Silks LA.
Fishpaugh JR.
Kastner ME.
J. Am. Chem. Soc.
1985,
107:
4679
<A NAME="RD03205ST-21B">21b</A>
Terang N.
Mehta BK.
Ila H.
Junjappa H.
Tetrahedron
1998,
54:
12973