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DOI: 10.1055/s-2006-939073
Efficient and Green Access to Functionalized and Highly Constrained Heteropolycyclic Derivatives via a Microwave-Accelerated Diels-Alder Cycloaddition and Heterogeneous Hydrogenation Sequence
Publikationsverlauf
Publikationsdatum:
24. April 2006 (online)
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Abstract
This paper describes an efficient and green access to functionalized and highly constrained heteropolycyclic derivatives via a microwave-accelerated cycloaddition and heterogeneous hydrogenation sequence.
Key words
microwave - cycloadditions - hydrogenation - heterogeneous catalysis - rhodium
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References and Notes
Microwave Irradiation Procedure: A mixture of 2H-pyran-2-one 1 (1 mmol) and N-substituted maleimide 2 (2.1 mmol) in distilled water (3 mL) was irradiated with microwaves (CEM Discover) for the time specified (final temperature 150 °C, power 100 W, ramp time 3 min). The temperature of the reaction was reduced to r.t.; the precipitated solid was filtered off and washed with water (0.5-1 mL). The anhydrous procedure was identical,
only no solvent was used.
N
-[9-Acetyl-1,2,3,3a,4,4a,5,6,7,7a,8,8a-dodecahydro-8-methyl-1,3,5,7-tetraoxo-4,8-ethenobenzo[1,2-
c
:4,5-
c
′]dipyrrol
-4-yl]benzamide (
3a). Mp > 358 °C (EtOH); IR (KBr): 1769, 1715, 1692, 1671, 1537 cm-1; 1H NMR (DMSO-d
6): δ = 1.86 (s, 3 H, Me), 2.15 (s, 3 H, COMe), 2.99 (d, 2 H, J = 8.3 Hz, 7a-H, 8a-H), 4.24 (d, 2 H, J = 8.3 Hz, 3a-H, 4a-H), 7.36 (s, 1 H, 10-H), 7.53 (m, 3 H, Ph), 7.89 (m, 2 H, Ph), 8.69 (s, 1 H, NHCOPh), 11.15 (s, 2 H, 2 × NH); 13C NMR (DMSO-d
6): δ = 18.1, 27.7, 41.0, 44.1, 50.3, 57.6, 127.5, 128.1, 131.1, 135.3, 138.8, 142.5, 167.4, 175.7, 177.0, 196.2; MS: m/z (%) = 421 (M+, 5), 105 (100); HRMS: m/z calcd for C22H19N3O6: 421.1273; found: 421.1262; Anal. Calcd for C22H19N3O6·0.8H2O: C, 60.63; H, 4.76; N, 9.64. Found: C, 60.74; H, 4.84; N, 9.29.
N
-[8-Acetyl-1,2,3,3a,4,4a,5,6,7,7a,8,8a-dodecahydro-2,6,8-trimethyl-1,3,5,7-tetraoxo-4,8-ethenobenzo[1,2-
c
: 4,5-
c
′]dipyrrol
-4-yl]benzamide (
3b). Mp 294-296 °C (EtOH); IR (KBr): 1767, 1697, 1679, 1661, 1540 cm-1; 1H NMR (DMSO-d
6): δ = 1.90 (s, 3 H, Me), 2.08 (s, 3 H, COMe), 2.69 (s, 6 H, 2 × Me), 3.11 (d, 2 H, J = 8.2 Hz, 7a-H, 8a-H), 4.31 (d, 2 H, J = 8.2 Hz, 3a-H, 4a-H), 7.20 (s, 1 H, 10-H), 7.56 (m, 3 H, Ph), 7.91 (m, 2 H, Ph), 8.75 (s, 1 H, NH); 13C NMR (DMSO-d
6): δ = 18.2, 24.3, 27.9, 41.2, 43.0, 49.0, 57.7, 127.5, 128.1, 131.2, 135.3, 138.1, 142.4, 167.7, 174.3, 175.5, 196.3; MS: m/z (%) = 449 (M+, 15), 105 (100); Anal. Calcd for C24H23N3O6·EtOH: C, 63.02; H, 5.90; N, 8.48. Found: C, 62.66; H, 5.55; N, 8.68.
The Rh precursor [Rh(cod)Cl]2 (0.25 mmol metal) and TPPTS or m-TPPTC ligand (1 mmol) were dissolved in deionized water (50 mL) and stirred for 12 h. After stirring, LDH (0.5 g) was added to the solution, and the resulting solution was stirred for 24 h. The solution was filtered, the solid was washed with deionized water, and dried under vacuum at r.t. The catalysts structures and the chemical composition were confirmed by XRD analysis and XPS spectroscopy.
17
Catalyst Tests; General Procedure. The tests were performed in a stirred stainless-steel autoclave using H2 pressures in the range 20-40 atm, catalyst (30 mg), and substrate 3 (30 mg) at different temperatures. All experiments were carried out in EtOAc. The reaction products were analyzed on a Knauer HPLC equipped with a chiral column EC 150/4 RESOLVOSIL BSA-7, UV-VIS detectors [MeCN-H3PO4 (0.1%), 1:3].
N
-[9-Acetyl-1,2,3,3a,4,4a,5,6,7,7a,8,8a-dodecahydro-8-methyl-1,3,5,7-tetraoxo-4,8-ethanobenzo[1,2-
c
:4,5-
c
′]dipyrrol
-4-yl]benzamide (
4a). 1H NMR (DMSO-d
6): δ = 1.66 (s, 3 H, Me), 1.90 (s, 3 H, COMe), 2.14 (d, 2 H, J = 6.4 Hz, 10-H), 2.42 (t, 1 H, J = 6.4 Hz, 9-H) 2.90 (d, 2 H, J = 8.1 Hz, 7a-H, 8a-H), 4.15 (d, 2 H, J = 8.1 Hz, 3a-H, 4a-H), 7.55 (m, 3 H, Ph), 7.90 (m, 2 H, Ph), 8.50 (s, 1 H, NHCOPh), 11.10 (s, 2 H, 2 × NH); 13C NMR (DMSO-d
6): δ = 18.0, 27.2, 32.4, 41.0, 41.8, 43.9, 49.7, 57.3, 127.6, 128.1, 131.3, 135.6, 167.9, 174.2, 175.6, 192.1; Anal. Calcd for C22H21N3O6: C, 62.41; H, 5.00; N, 9.92. Found: C, 62.53; H, 4.94; N, 9.90.
N
-[9-Acetyl-1,2,3,3a,4,4a,5,6,7,7a,8,8a-dodecahydro-2,6,8-trimethyl-1,3,5,7-tetraoxo-4,8-ethanobenzo[1,2-
c
:4,5-
c
′]dipyrrol
-4-yl]benzamide (
4b). 1H NMR (DMSO-d
6): δ = 1.69 (s, 3 H, Me), 1.83 (s, 3 H, COMe), 2.09 (d, 2 H, J = 6.6 Hz, 10-H), 2.40 (t, 1 H, J = 6.6 Hz, 9-H) 2.75 (s, 6 H, 2 × Me), 2.98 (d, 2 H, J = 8.1 Hz, 7a-H, 8a-H), 4.22 (d, 2 H, J = 8.1 Hz, 3a-H, 4a-H), 7.57 (m, 3 H, Ph), 7.89 (m, 2 H, Ph), 8.53 (s, 1 H, NHCOPh); 13C NMR (DMSO-d
6): δ = 17.9, 24.2, 27.5, 32.9, 40.8, 41.5, 44.2, 48.5, 56.6, 127.4, 128.0, 131.3, 135.1, 167.0, 173.5, 175.1, 190.1. Anal. Calcd for C24H25N3O6: C, 63.85; H, 5.58; N, 9.31. Found: C, 63.50; H, 5.55; N, 9.08.
N
-[1,2,3,3a,4,4a,5,6,7,7a,8,8a-dodecahydro-9-(1-hydroxyethyl)-2,6,8-trimethyl-1,3,5,7-tetraoxo-4,8-ethenobenzo[1,2-
c
:4,5-
c
′]dipyrrol
-4-yl]benzamide (
5b). 1H NMR (DMSO-d
6): δ = 1.23 (d, 3 H, J = 6.8 Hz, CH
3CHOH), 1.83 (s, 3 H, Me), 2.72 (s, 6 H, 2 × Me), 2.80 (s, 1 H, OH), 3.01 (d, 2 H, J = 8.1 Hz, 7a-H, 8a-H), 4.06 (q, 1 H, J = 6.8 Hz, CHOH), 4.29 (d, 2 H, J = 8.1 Hz, 3a-H, 4a-H), 6.71 (s, 1 H, 10-H), 7.55 (m, 3 H, Ph), 7.90 (m, 2 H, Ph), 8.74 (s, 1 H, NHCOPh); 13C NMR (DMSO-d
6): δ = 18.1, 24.1, 24.5, 40.9, 42.7, 50.1, 57.4, 74.6, 127.5, 128.1, 131.0, 135.2, 138.0, 143.7, 167.6, 174.8, 176.6. Anal. Calcd for C24H25N3O6: C, 63.85; H, 5.58; N, 9.31. Found: C, 64.04; H, 5.97; N, 9.68.