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 2015; 26(16): 2247-2252
DOI: 10.1055/s-0035-1560051
DOI: 10.1055/s-0035-1560051
letter
N,N,N-Triphenylselenylisocyanuric Acid (TPSCA): A New Versatile Reagent for α-Phenylselenenylation of Aldehydes and Ketones
Weitere Informationen
Publikationsverlauf
Received: 22. April 2015
Accepted after revision: 03. Juli 2015
Publikationsdatum:
19. August 2015 (online)
![](https://www.thieme-connect.de/media/synlett/201516/lookinside/thumbnails/st-2015-d0297-l_10-1055_s-0035-1560051-1.jpg)
Abstract
A new, versatile reagent, N,N,N-triphenylselenyl-isocyanuric acid (TPSCA) has been prepared, characterized, and used as a source of the electrophilic phenylselenyl group. This relatively stable compound was utilized for an efficient α-selenenylation reaction of aldehydes and ketones catalyzed by l-prolinamide under mild reaction conditions. The organocatalytic asymmetric α-selenenylation of an aldehyde was also studied and the reaction was found to proceed with high enantioselectivity (96% ee).
Supporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0035-1560051.
- Supporting Information
-
References and Notes
- 1a Santi C. Organoselenium Chemistry: Between Synthesis and Biochemistry. Bentham Science Pub.; Oak Park (USA): 2014
- 1b Liotta D. Organoselenium Chemistry. Wiley; New York: 1987
- 1c Back TG. Organoselenium Chemistry: A Practical Approach. Oxford University Press; Oxford: 1999
- 2 Back TG. Electrophilic Selenium Reactions. In Organoselenium Chemistry. Liotta D. Wiley; New York: 1987. Chap. 1
- 3a Sharpless KB, Young MW. J. Org. Chem. 1975; 40: 947
- 3b Reich HJ, Renga JM, Reich IL. J. Am. Chem. Soc. 1975; 95: 5434
- 3c Clive DL. J. Chem. Soc., Chem. Commun. 1973; 695
- 4 Lerouge P, Paulmier C. Tetrahedron Lett. 1984; 25: 1987
- 5 Shea RG, Fitzner JN, Fankhauser JE, Spaltenstein A, Carpino PA, Peevey RM, Pratt DV, Tenge BJ, Hopkins PB. J. Org. Chem. 1986; 51: 5243
- 6 Miniejew C, Outurquin F, Pannecoucke X. Tetrahedron 2005; 61: 447
- 7 Lerouge P, Paulmier C. Tetrahedron Lett. 1984; 25: 1983
- 8 Fitzner JN, Shea RG. Fankhauser J. E, Hopkins PB. J. Org. Chem. 1985; 50: 417
- 9a Schreiber SL, Santini C. J. Am. Chem. Soc. 1984; 106: 4038
- 9b Marshall JA, Royce RD. J. Org. Chem. 1982; 47: 693
- 10a Nicolaou KC, Claremon DA, Barnette WE, Seitz SP. J. Am. Chem. Soc. 1979; 101: 3704
- 10b Wang J, Li H, Mei Y, Lou B, Xu D, Xie D, Guo H, Wang W. J. Org. Chem. 2005; 70: 5678
- 11a Hori T, Sharpless KB. J. Org. Chem. 1979; 44: 4204
- 11b Hori T, Sharpless KB. J. Org. Chem. 1979; 44: 4208
- 11c Frejd T, Sharpless KB. Tetrahedron Lett. 1978; 2239
- 11d Denmark ES, Collins RW. Org. Lett. 2007; 9: 3801
- 12 Tingoli M, Diana M, Panunzi B. Tetrahedron Lett. 2006; 47: 7529
- 13a Sulzer-Mossé S, Alexakis A. Chem. Commun. 2007; 3123
- 13b Grondal D, Enders D, Hüttl MR. M. Angew. Chem. Int. Ed. 2007; 46: 1570
- 13c Marigo M, Jørgensen KA. Chem. Commun. 2006; 2001
- 13d List B. Chem. Commun. 2006; 819
- 14a Berkessel A, Groger H. Asymmetric Organocatalysis: From Biomimetic Concepts to Applications in Asymmetric Synthesis. Wiley-VCH; Weinheim: 2005
- 14b Northrup AB, Mangion IK, Hettche F, MacMillan DW. C. Angew. Chem. Int. Ed. 2004; 43: 2152
- 14c Córdova A, Barbas CF. III. Tetrahedron Lett. 2003; 44: 1923
- 14d List B. J. Am. Chem. Soc. 2002; 124: 5656
- 14e Zhong G. Angew. Chem. Int. Ed. 2003; 42: 4247
- 15a Lelais G, MacMillan DW. C. Aldrichimica Acta 2006; 39: 79 ; and references cited therein
- 15b Ibrahem I, Rios R, Vesely J, Zhao G.-L, Córdova A. Chem. Commun. 2007; 849
- 15c Dinér P, Nielsen M, Marigo M, Jørgensen KA. Angew. Chem. Int. Ed. 2007; 46: 1983
- 15d Sundén H, Rios R, Córdova A. Tetrahedron Lett. 2007; 48: 7865
- 15e Zhao G.-L, Rios R, Vesely J, Eriksson L, Córdova A. Angew. Chem. Int. Ed. 2008; 47: 8468
- 15f Tiecco M, Carlone A, Sternativo S, Marini F, Bartoli G, Melchiorre P. Angew. Chem. Int. Ed. 2007; 46: 6882
- 16a Veisi H. Synthesis 2010; 2631
- 16b De Luca L, Giacomelli G, Nieddu G. Synlett 2005; 223
- 16c Mendonca GF, Sindra HC, de Almeida LS, Esteves PM, de Mattos MC. S. Tetrahedron Lett. 2009; 50: 473
- 16d Hirai N, Kagayama T, Tatsukawa Y, Sakaguchi S, Ishii Y. Tetrahedron Lett. 2004; 45: 8277
- 16e Vilhelmesn MH, Andersson AS, Nielsen MB. Synthesis 2009; 1469
- 16f de Almeida LS, Esteves PM, de Mattos MC. S. Tetrahedron Lett. 2009; 50: 3001
- 17a de Almeida LS, Esteves PM, de Mattos MC. S. Synthesis 2006; 221
- 17b Mendonça GF, de Mattos MC. S. Quim. Nova 2008; 31: 798
- 18 Tozetti SD. F, de Almeida LS, Esteves PM, de Mattos MC. S. J. Braz. Chem. Soc. 2007; 18: 675
- 19 Preparation of N,N,N-(Triphenylselenyl)isocyanuric Acid (TPSCA, 3): Cyanuric acid (1; 0.129 g, 1 mmol) was added to a solution of KOH (0.168 g, 3 mmol) in H2O (10 mL). The mixture was heated to 90 °C for 30 min, and then cooled to room temperature. A solution of silver nitrate (0.850 g, 5 mmol) in H2O (10 mL) was added dropwise, with stirring, to the above mixture. After 1 h, the white precipitate was collected by filtration, washed with water, and dried at 105 °C to give the silver salt of isocyanuric acid 2 (0.337 g, 75%) as a white solid. The anhydrous silver salt 2 (0.90 g, 2 mmol) was added to a solution of phenylselenyl bromide24 (1.652 g, 7 mmol) in anhydrous CH2Cl2 (10 mL), and the mixture was stirred at room temperature under an argon atmosphere. After 2 h, precipitated AgBr was filtered off and the filtrate was evaporated under reduced pressure; anhydrous n-hexane (10 mL) was added, and the crude solid product was collected and subjected to preparative TLC (silica gel; n-hexane–EtOAc, 4:1) to afford TPSCA 3 (0.89 g, 75%) as a white solid; mp 143–145 °C. IR (KBr): 1703 cm–1. 1H NMR (300 MHz, DMSO-d6): δ = 7.82 (s, 6 H), 7.57 (s, 9 H). 13C NMR (75 MHz, DMSO-d6): δ = 148.9, 131.7, 129.1, 125.9. MS: m/z = 597 [80Se3]. Anal. Calcd for C21H15N3O3Se3: C, 42.21; H, 2.51; N, 7.03. Found: C, 41.97; H, 2.81; N, 6.13.
- 20a Northrup AB, Mangion IK, Hettche F, MacMillan DW. C. Angew. Chem. Int. Ed. 2004; 43: 2152
- 20b Córdova A, Barbas III CF. Tetrahedron Lett. 2003; 44: 1923
- 20c Hayashi Y, Tsuboi W, Shoji M, Suzuki N. J. Am. Chem. Soc. 2003; 125: 11208
- 20d Hayashi Y, Yamaguchi J, Sumiya T, Shoji M. Angew. Chem. Int. Ed. 2004; 43: 1112
- 21a Sakthivel K, Nortz W, Bui T, Barbas CF. III. J. Am. Chem. Soc. 2001; 123: 5260
- 21b Allemann C, Gordillo R, Clemente FR, Cheong PH.-Y, Houk KN. Acc. Chem. Res. 2004; 37: 558
- 22 General Procedure for α-Selenenylation of Aldehydes and Ketones: To a solution of aldehyde or ketone (3 mmol) and l-prolinamide (5 mol%) in anhydrous CH2Cl2 (6 mL), was added TPSCA 3 (1 mmol) at room temperature. The mixture was stirred in the presence of 4Ǻ molecule sieves under an argon atmosphere for the appropriate time (Table 2). When the reaction was complete (TLC), the reaction mixture was treated with water (5 mL) and the solution was extracted with ethyl acetate (3 × 15 mL). The combined extracts were dried over MgSO4, filtered, and concentrated in vacuo. The resulting residue was further purified by preparative TLC (silica gel; n-hexane). The identity and purity of the products were confirmed by IR, 1H NMR, and 13C NMR spectroscopic analysis. 2-(Phenylseleno)heptanal (5b) Yield: 0.59 g (78%); pale-yellow oil. IR (neat): 1709 cm–1. 1H NMR (300 MHz, CDCl3): δ = 9.39 (d, J = 3.7 Hz, 1 H), 7.58–7.49 (m, 2 H), 7.34–7.25 (m, 3 H), 3.63–3.57 (m, 1 H), 1.72–1.43 (m, 4 H), 1.33–1.28 (m, 4 H), 0.89 (t, J = 6.6 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 193.3, 136.0, 129.33, 129.32, 126.4, 53.2, 31.6, 28.1, 28.0, 22.9, 14.3. 3-Phenyl-2-(phenylseleno)propionaldehyde (5d) Yield: 0.73 g (84%); pale-yellow oil. IR (neat): 1688 cm–1. 1H NMR (300 MHz, CDCl3): δ = 9.48 (d, J = 4.0 Hz, 1 H), 7.39 (d, J = 7.5 Hz, 2 H), 7.25–6.95 (m, 6 H), 6.86–6.75 (m, 2 H), 3.95–3.84 (m, 1 H), 3.36 (dd, J = 10.9, 8.0 Hz, 1 H), 3.03 (dd, J = 10.9, 6.0 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 194.6, 138.0, 134.5, 131.5, 129.4, 129.0, 128.9, 126.3, 45.3, 28.1. 2-(Phenylselenyl)cyclopentanone (5i) Yield: 0.55 g (75%); pale-yellow oil. IR (neat): 1730 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.94 (dd, J = 6.5, 1.5 Hz, 2 H), 7.62–7.44 (m, 3 H), 3.77–3.74 (m, 1 H), 2.32–2.27 (m, 2 H), 2.04–1.92 (m, 4 H). 13C NMR (75 MHz, CDCl3): δ = 211.0, 134.4, 128.6, 128.0, 127.4, 45.7, 35.6, 29.6, 20.0. 1-Methyl-3-(phenylselenyl)piperidin-4-one (5k) Yield: 0.65 g (80%); pale-orange oil. IR (neat): 1709 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.60–7.55 (m, 2 H), 7.33–7.16 (m, 3 H), 3.80 (br s, 1 H), 3.36–3.30 (m, 1 H), 3.21–3.17 (m, 1 H), 2.90–2.80 (m, 2 H), 2.49–2.46 (m, 1 H), 2.24 (s, 3 H), 2.19–2.15 (m, 1 H). 13C NMR (75 MHz, CDCl3): δ = 205.58, 134.4, 129.9, 129.7, 128.6, 61.5, 55.6, 50.2, 45.8, 37.1. 2-(Phenylselenyl)pentan-3-one (5l) Yield: 0.53 g (73%); pale-yellow oil. IR (neat): 1702 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.53–7.50 (m, 2 H), 7.35–7.26 (m, 3 H), 3.82 (q, J = 7.0 Hz, 1 H), 2.80 (dq, J = 17.3, 7.3 Hz, 1 H), 2.50 (dq, J = 17.3, 7.3 Hz, 1 H), 1.49 (d, J = 7.0, 3 H), 1.08 (t, J = 7.3 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 207.6, 135.8, 128.9, 128.7, 127.1, 45.0, 33.0, 16.5, 8.4. 1-Phenyl-2-(phenylselanyl)propanone (5m) Yield: 0.62 g (72%); pale-orange oil. IR (neat): 1673 cm–1. 1H NMR (300 MHz, CDCl3): δ = 7.87 (d, J = 8.7 Hz, 2 H), 7.54–7.40 (m, 6 H), 7.29–7.26 (m, 2 H), 4.70 (q, J = 6.8 Hz, 1 H), 1.65 (d, J = 6.8 Hz, 3 H). 13C NMR (75 MHz, CDCl3): δ = 196.3, 137.0, 136.6, 133.0, 132.8, 129.0, 129.3, 129.0, 128.9, 128.7, 39.7, 17.6.
- 23 Nazari M, Movassagh B. Tetrahedron Lett. 2009; 50: 1453
- 24 Yu L, Wang J, Chen T, Wang Y, Xu Q. Appl. Organomet. Chem. 2014; 28: 652