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Synlett 2015; 26(01): 95-100
DOI: 10.1055/s-0034-1379494
DOI: 10.1055/s-0034-1379494
letter
2-Aminobenzimidazole Organocatalyzed Asymmetric Amination of Cyclic 1,3-Dicarbonyl Compounds
Further Information
Publication History
Received: 19 September 2014
Accepted after revision: 18 October 2014
Publication Date:
27 November 2014 (online)
Dedicated to the memory of Prof. Carlos F. Barbas III
Abstract
The use of a trans-cyclohexanediamine benzimidazole derivative as a hydrogen-bond catalyst for the electrophilic amination of cyclic 1,3-dicarbonyl compounds is herein presented. High yields and enantioselectivities varying from moderate to excellent are generally obtained using mild reaction conditions and as low as 1 mol% of catalyst loading.
Key words
organocatalysis - electrophilic amination - asymmetric catalysis - dicarbonyl compounds - benzimidazoleSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0034-1379494.
- Supporting Information
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References
- 1a Broggini G, Borsini E, Piarulli U In Science of Synthesis, Cross-Coupling and Heck-Type Reactions. Vol. 3. Molander GA, Wolfe JP, Larhed M. Thieme; Stuttgart: 2013: 521-583
- 1b Christoffers J, Mann A. Angew. Chem. Int. Ed. 2001; 40: 4591
- 1c Corey EJ, Guzman-Perez A. Angew. Chem. Int. Ed. 1998; 37: 389
- 2 Ciganek E In Organic Reactions. Vol. 72. Denmark SE. Wiley; New Jersey: 2008: 1-366
- 3a Erdik E. Tetrahedron 2004; 60: 8747
- 3b Greck C, Drouillat B, Thomassigny C. Eur. J. Org. 2004; 1377
- 3c Guillena G, Ramón DJ. Tetrahedron: Asymmetry 2006; 17: 1465
- 3d Vilaivan T, Bhanthumnavin W. Molecules 2010; 15: 917
- 3e Vallribera A, Sebastian RM, Shafir A. Curr. Org. Chem. 2011; 15: 1539
- 3f Russo A, De Fusco C, Lattanzi A. RSC. Adv. 2012; 2: 385
- 3g Chauhan P, Chimni SS. Tetrahedron: Asymmetry 2013; 24: 343
- 4 Marigo M, Juhl K, Jørgensen KA. Angew. Chem. Int. Ed. 2003; 42: 1367
- 5a Foltz C, Stecker B, Marconi G, Bellemin-Laponaz S, Wadepohl H, Gade LH. Chem. Commun. 2005; 5115
- 5b Kang YK, Kim DY. Tetrahedron Lett. 2006; 47: 4565
- 5c Mashiko T, Kumagai N, Shibasaki M. J. Am. Chem. Soc. 2009; 131: 14990
- 5d Mang JY, Kwon DG, Kim DY. Bull. Korean Chem. Soc. 2009; 30: 249
- 5e Ghosh S, Nandakumar MV, Krautscheid H, Schneider C. Tetrahedron Lett. 2010; 51: 1860
- 5f Torres M, Maisse-François A, Bellemin-Laponaz S. ChemCatChem 2013; 5: 3078
- 6a Saaby S, Bella M, Jørgensen KA. J. Am. Chem. Soc. 2004; 126: 8120
- 6b Pihko PM, Pohjakallio A. Synlett 2004; 2115
- 6c Liu X, Li H, Deng L. Org. Lett. 2005; 7: 169
- 6d Santacruz L, Niembro S, Santillana A, Shafir A, Vallribera A. New J. Chem. 2014; 38: 636
- 7a He R, Wang X, Hashimoto T, Maruoka K. Angew. Chem. Int. Ed. 2008; 47: 9466
- 7b Lan Q, Wang X, He R, Ding C, Maruoka K. Tetrahedron Lett. 2009; 50: 3280
- 7c He R, Maruoka K. Synthesis 2009; 2289
- 8a Xu X, Yabuta T, Yuan P, Takemoto Y. Synlett 2006; 137
- 8b Terada M, Nakano M, Ube H. J. Am. Chem. Soc. 2006; 128: 16044
- 8c Jung SH, Kim DY. Tetrahedron Lett. 2008; 49: 5527
- 8d Konishi H, Lam TY, Malerich JP, Rawal VH. Org. Lett. 2010; 12: 2028
- 8e Han X, Zhong F, Lu Y. Adv. Synth. Catal. 2010; 352: 2778
- 8f Zhang Z.-H, Dong X.-Q, Tao H.-Y, Wang C.-J. ARKIVOC 2011; (ii): 137
- 8g Inokuma T, Furukawa M, Uno T, Suzuki Y, Yoshida K, Yano Y, Matsuzaki K, Takemoto Y. Chem. Eur. J. 2011; 17: 10470
- 8h Murai K, Fukushima S, Nakamura A, Shimura M, Fujioka H. Tetrahedron 2011; 67: 4862
- 9a Almasi D, Alonso DA, Gómez-Bengoa E, Nájera C. J. Org. Chem. 2009; 74: 6163
- 9b Gómez-Torres E, Alonso DA, Gómez-Bengoa E, Nájera C. Org. Lett. 2011; 13: 6106
- 9c Gómez-Torres E, Alonso DA, Gómez-Bengoa E, Nájera C. Eur. J. Org. Chem. 2013; 1434
- 9d Trillo P, Baeza A, Nájera C. Synthesis 2014; in press; DOI: 10.1055/s-0034-1378618
- 10 General Procedure for the Asymmetric Amination of Cyclic 1,3-Dicarbonyl Compounds: In a tube, open to the atmosphere, in a thermostated bath (25 °C) the requisite 1,3-dicarbonyl compound (0.2 mmol) was added to a solution of organocatalyst II (0.002 mmol, 1 mol%) in Et2O (1 mL). After 5 min, di-tert-butylazodicarboxylate (2a; 0.21 mmol, 1.05 equiv) was added in one portion and the reaction was then allowed to react for 10 h. After this time, H2O (5 mL) and EtOAc were added, and then the aqueous layer was re-extracted with EtOAc (2 × 5 mL). The combined organic phases were dried (MgSO4), filtered and the solvent was evaporated under reduced pressure. Finally, the crude product was purified by flash chromatography using hexanes–EtOAc mixtures as eluent.Physical and spectroscopic data given below are for compound 3da and may be taken as representative. For further details; see Supporting Information. Di-tert-butyl 1-[2-(Ethoxycarbonyl)-1-oxo-1,2,3,4-tetrahydronaphthalen-2-yl]hydrazine-1,2-dicarboxylate (3da) 8b Slightly yellow viscous oil (88 mg, 98% yield, 91% ee); [α]D 28 +23.3 (c = 2.0, CHCl3). 1H NMR (300 MHz): δ = 1.33 (br m, 21 H), 2.67 (m, 1 H), 2.95 (m, 2 H), 3.44 (br m, 1 H), 4.31 (q, J = 7.0 Hz, 2 H), 6.23 (m, 1 H), 7.25 (m, 2 H), 7.46 (m, 1 H), 7.95 (dd, J = 28.0, 7.2 Hz, 1 H). 13C NMR (75 MHz): δ = 14.1, 25.6, 27.7, 28.0, 31.1, 60.3, 61.9, 80.8, 82.7, 126.4, 127.7, 128.5, 131.7, 133.4, 154.4, 155.5, 169.5, 191.0. MS (IE): m/z (%) = 348 (6.5) [M+ – Boc], 292 (47), 219 (100), 175 (86), 158 (30). Chiral HPLC analysis: Chiralcel IA column, hexane–i-PrOH (85:15), flow rate = 1 mL/min, λ = 254 nm, retention times: tR = 8.0, 11.5 min.
- 11 (S)-3aa [α]D 29 +3.8 (c = 1, CHCl3, 92% ee). Reported value in ref. 5b for R-enantiomer: [α]D 32 –3.47 (c = 1.09, CHCl3, 97% ee). See Supporting Information for further details.
For selected reviews about electrophilic amination, see:
For selected examples of metal-catalyzed electrophilic amination of 1,3-dicarbonyl compounds with diazocarboxylates, see:
For selected examples of electrophilic amination of 1,3-dicarbonyl compounds with diazocarboxylates using chiral amines as organocatalysts, see:
For selected examples of electrophilic amination of 1,3-dicarbonyl compounds with diazocarboxylates using phase-transfer catalysts, see:
For selected examples of electrophilic amination of 1,3-dicarbonyl compounds with diazocarboxylates using hydrogen-bond catalysis, see:
For recent publications, see: