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DOI: 10.1055/s-0029-1218300
Association of Intramolecular Furan Diels-Alder Reaction and N-Acyliminium Alkylation for the Synthesis of Pentacyclic Precursor of Aromathecins
Publikationsverlauf
Publikationsdatum:
21. Oktober 2009 (online)
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Abstract
A new approach for the synthesis of isoindoloquinoline and aromathecin templates is presented. These were obtained in a few steps starting from inexpensive reagents by two different strategies. The key step for both sequences was the IMFDA reaction, leading diastereoselectively to the formation of the unsaturated DE ring system of the expected alkaloid skeletons.
Key words
benzoindolizino[1,2-b]quinolinone - heterocycle - N-acyliminium - α-amidoalkylation - Diels-Alder
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References and Notes
Data for 2A
Mp
123 ˚C (white solid); R
f
= 0.27 (cyclohexane-EtOAc = 1:1).
IR: ν = 1729 (C=O), 1684 (C=O),
1645 (C=C), 1444 (CH), 1426 (CH), 1290 (CO) cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 1.12-1.24
(m, 1 H, H6
α), 1.20 (t, 3 H, CH3CH2, J = 7.0 Hz),
2.37-2.47 (m, 1 H, H7), 2.63-2.75 (m,
1 H, H6
β), 2.68-2.75 (m,
1 H, H8), 3.70 (d, 1 H, H4
α, J = 15.6 Hz),
4.10 (q, 2 H, CH3CH2, J = 7.0
Hz), 4.41 (dd, 1 H, H5, J = 12.5,
3.1 Hz), 4.90 (d, 1 H, H4
β, J = 15.6 Hz),
5.10 (dd, 1 H, H1, J = 4.7,
1.6 Hz), 6.28 (d, 1 H, H3, J = 5.5
Hz), 6.42 (dd, 1 H, H2, J = 5.5,
1.6 Hz), 7.38-7.55 (m, 3 H, Har), 7.83 (d, 1
H, Har, J = 7.0
Hz). ¹³C NMR (50 MHz, CDCl3): δ = 14.4 (CH3),
36.6 (C6), 39.6 (C7), 41.1 (C4),
53.7 (C8), 57.5 (C5), 61.1 (CH2 ester),
80.1 (C1), 85.7 (Cq), 122.0 (CHar),
124.2 (CHar), 128.6 (CHar), 131.6 (CHar),
132.5 (Cq), 136.7 (C3), 137.7 (C2),
145.2 (Cq), 166.7 (C=O), 171.5 (C=O).
Anal. Calcd for C19H19NO4 (325.13):
C, 70.14; H, 5.89; N, 4.31. Found: C, 69.98; H, 5.66; N, 4.21.
Only traces of product 24 were detected by ¹H NMR.
20
Data for 3A
Mp
159 ˚C (white solid); R
f
= 0.23 (cyclohexane-EtOAc = 2:3).
IR: ν = 2903 (CH), 1731 (C=O), 1692 (C=O),
1636 (C=N), 1508 (C=C) cm-¹. ¹H
NMR (200 MHz, CDCl3): δ = 1.21-1.31
(m, 1 H, H11
α), 1.24 (t, 3 H, CH3CH2, J = 7.0 Hz), 2.42-2.53
(m, 1 H, H12), 2.77 (dd, 1 H, H13, J = 4.7, 3.9
Hz), 2.96-3.08 (m, 1 H, H11
β),
3.77 (d, 1 H, H4
α, J = 14.9
Hz), 4.10 (q, 2 H, CH3CH2, J = 7.0
Hz), 4.60 (dd, 1 H, H5, J = 12.1,
2.7 Hz), 5.02 (d, 1 H, H4
β, J = 14.9 Hz),
5.13 (dd, 1 H, H1, J = 3.9,
1.6 Hz), 6.30 (d, 1 H, H3, J = 6.3
Hz), 6.47 (dd, 1 H, H2, J = 6.3,
1.6 Hz), 7.62 (dd, 1 H, H8, J = 7.8,
7.0 Hz), 7.78-7.86 (m, 1 H, H7), 7.98 (d, 1
H, H9, J = 7.8
Hz), 8.14 (d, 1 H, H6, J = 8.6
Hz), 8.62 (s, 1 H, H10). ¹³C
NMR (50 MHz, CDCl3): δ 14.4 (CH3),
35.3 (C11), 39.6 (C12), 41.2 (C4), 53.7
(C13), 58.9 (C5), 61.1 (CH2 ester),
80.2 (C1), 85.5 (Cq), 123,8 (Cq),
127.3 (C8), 127.9 (Cq), 129.4 (C6),
129.8 (C9), 131.7 (C7), 133.2 (C10),
137.1 (C3), 137.4 (C2), 149.8 (Cq), 163.2
(C=N), 164.9 (C=O), 171.3 (C=O). Anal.
Calcd for C22H20N2O4 (376.41):
C, 70.20; H, 5.36; N, 7.44. Found: C, 70.05; H, 5.16; N, 7.28.