RSS-Feed abonnieren
Bitte kopieren Sie die angezeigte URL und fügen sie dann in Ihren RSS-Reader ein.
https://www.thieme-connect.de/rss/thieme/de/10.1055-s-00000083.xml
Synlett 2014; 25(5): 724-728
DOI: 10.1055/s-0033-1340673
DOI: 10.1055/s-0033-1340673
letter
Copper Hydride Catalyzed Reductive Aldol Addition/Lactonization Domino Reactions of α,β-Unsaturated Diesters
Weitere Informationen
Publikationsverlauf
Received: 25. November 2013
Accepted after revision: 05. Januar 2014
Publikationsdatum:
27. Januar 2014 (online)
![](https://www.thieme-connect.de/media/synlett/201405/lookinside/thumbnails/10.1055-s-0033-1340673-1.jpg)
Abstract
The first copper-catalyzed reductive aldol addition/lactonization domino reactions of α,β-unsaturated dicarboxylate esters with ketones were achieved in high yields. The method, which involves easily available reagents, a flexible combination of reactants, and mild conditions, provides a simple route to functionalized lactones bearing an ester group.
-
References and Notes
- 1 Chiu P. Synthesis 2004; 2210
- 2 Deutsch C, Lipshutz BH, Krause N. Angew. Chem. Int. Ed. Engl. 2007; 46: 1650
- 3 Deutsch C, Krause N, Lipshutz BH. Chem. Rev. 2008; 108: 2916
- 4 Li Z, Liu G, Chiu P. Huaxue Jinzhan 2008; 20: 1909 ; Chem. Abstr. 2009, 151, 100615
- 5 Mahoney WS, Brestensky DM, Stryker JM. J. Am. Chem. Soc. 1988; 110: 291
- 6 Brestensky DM, Stryker JM. Tetrahedron Lett. 1989; 30: 5677
- 7 Koenig TM, Daeuble JF, Brestensky DM, Stryker JM. Tetrahedron Lett. 1990; 31: 3237
- 8 Kamenecka TM, Overman LE, Ly Sakata SK. Org. Lett. 2002; 4: 79
- 9 Chiu P, Chen B, Cheng KF. Tetrahedron Lett. 1998; 39: 9229
- 10 Chiu P, Szeto CP, Geng Z, Cheng K.-F. Org. Lett. 2001; 3: 1901
- 11 Baker BA, Bošković ZV, Lipshutz BH. Org. Lett. 2008; 10: 289
- 12 Welle A, Cirriez V, Riant O. Tetrahedron 2012; 68: 3435
- 13 Li N, Ou J, Miesch M, Chiu P. Org. Biomol. Chem. 2011; 9: 6143
- 14 Ou J, Wong W.-T, Chiu P. Org. Biomol. Chem. 2012; 10: 5971
- 15 Ou J, Wong W.-T, Chiu P. Tetrahedron 2012; 68: 3450
- 16 Lam HW, Joensuu PM. Org. Lett. 2005; 7: 4225
- 17 Zhao D, Oisaki K, Kanai M, Shibasaki M. Tetrahedron Lett. 2006; 47: 1403
- 18 Chuzel O, Deschamp J, Chausteur C, Riant O. Org. Lett. 2006; 8: 5943
- 19 Deschamp J, Chuzel O, Hannedouche J, Riant O. Angew. Chem. Int. Ed. 2006; 45: 1292
- 20 Welle A, Díez-González S, Tinant B, Nolan SP, Riant O. Org. Lett. 2006; 8: 6059
- 21 Zheng A.-J, Shan F.-J, Li Z.-N, Li Z.-C, Jiang L. Chem. Pap. 2013; 67: 1271
- 22 Zheng A, Jiang L, Li Z. Chin. J. Chem. 2012; 30: 2587
- 23 Li Z, Jiang L, Li Z, Chen H. Chin. J. Chem. 2013; 31: 539
- 24 Du Y, Xu L.-W, Shimizu Y, Oisaki K, Kanai M, Shibasaki M. J. Am. Chem. Soc. 2008; 130: 16146
- 25 For a report on a cobalt-catalyzed aldol addition/lactonization from a maleate monoester monamide, see: Lumby RJ. R, Joensuu PM, Lam HW. Org. Lett. 2007; 9: 4367
- 26 Chiu P, Li ZN, Fung KC. M. Tetrahedron Lett. 2003; 44: 455
- 27 Methyl 2-Methyl-5-oxo-2-phenyltetrahydrofuran-3-carboxylate: Typical Procedure A dried Schlenk tube was charged with CuF(PPh3)3·2MeOH (5.9 mg, 0.0063 mmol), Xantphos (5.6 mg, 0.0097 mmol), and THF (2.0 mL) under N2. The mixture was stirred for 30 min and then PMHS (0.15 mL, 2.5 mmol) was added, and the mixture was stirred for a further 15 min. A soln of ketone 3a (84 mg, 0.70 mmol) and dimethyl maleate (137 mg, 0.951 mmol) in THF (2 × 0.5 mL) was added, and the mixture was stirred until 3a was almost consumed (GC). The reaction was quenched by addition of a 0.3 M soln of NH4F in 3:1 MeOH–H2O (10 mL). The syn/anti ratio of 4a (66.9:33.1) was then determined by GC. Column chromatography [silica gel, PE–EA (100:0 to 85:15)] gave a diastereomeric mixture of the products as a colorless liquid; yield: 153 mg (93%). Further chromatographic separation gave pure anti-4a and syn-4a. �anti-4a: colorless oil. Rf = 0.50 (EA–PE, 30:70). 1H NMR (400 MHz, CDCl3): δ = 7.46–7.31 (m, 5 H), 3.82 (s, 3 H), 3.60–3.49 (m, 1 H), 2.98 (dd, J = 17.8, 5.1 Hz, 1 H), 2.63 (ddd, J = 17.7, 8.7, 0.9 Hz, 1 H), 1.67 (d, J = 0.8 Hz, 3 H). 13C NMR (101 MHz, CDCl3): δ = 174.42, 171.11, 143.74, 128.84, 128.22, 124.29, 86.96, 52.60, 51.60, 32.04, 25.38. LRMS (EI, 70 ev): m/z (%) = 234 (10, M+), 219 (4), 175 (4), 131 (9), 114 (100), 77 (24), 55 (27), 27 (3). �syn-4a: colorless oil. Rf = 0.43 (EA–PE, 30:70). 1H NMR (400 MHz, CDCl3): d = 7.40–7.24 (m, 5 H), 3.46 (t, J = 7.8 Hz, 1 H), 3.33 (s, 3 H), 3.02 (dd, J = 17.9, 7.0 Hz, 1 H), 2.82 (dd, J = 17.9, 8.7 Hz, 1 H), 1.93 (s, 3 H). 13C NMR (101 MHz, CDCl3): δ = 174.52, 169.99, 139.83, 128.46, 128.40, 124.91, 87.23, 52.72, 52.08, 32.01, 28.72. LRMS (EI, 70 ev): m/z (%) = 219 (13), 191 (8), 160 (3), 114 (100), 77 (27), 55 (28), 27 (3).�
- 28 The relative configurations of the 4a diastereoisomers were deduced by base-catalyzed isomerization of the product mixture and by NOSEY spectroscopy. DBU-catalyzed isomerization of mixtures of 4a with syn/anti ratios of 68:32 or 54:46 in refluxing toluene each gave a mixture with a 37:63 syn/anti ratio.
- 29 Shono T, Hamaguchi H, Nishiguchi I, Sasaki M, Miyamoto T, Miyamoto M, Fujita S. Chem. Lett. 1981; 1217
- 30 Pohmakotr M, Sampaongoen L, Issaree A, Tuchinda P, Reutrakul V. Tetrahedron Lett. 2003; 44: 6717
- 31 Pohmakotr M, Komutkul T, Tuchinda P, Prabpai S, Kongsaeree P, Reutrakul V. Tetrahedron 2005; 61: 5311
- 32 The stereochemistries of the 6a isomers were deduced from their NOESY spectra.