Subscribe to RSS
Please copy the URL and add it into your RSS Feed Reader.
https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000084.xml
Synthesis 2017; 49(02): 319-325
DOI: 10.1055/s-0036-1589408
DOI: 10.1055/s-0036-1589408
paper
Concentration Effect in the Asymmetric Michael Addition of Acetone to β-Nitrostyrenes Catalyzed by Primary Amine Thioureas
Further Information
Publication History
Received: 28 September 2016
Accepted after revision: 07 October 2016
Publication Date:
14 November 2016 (online)
Dedicated to Professor Dieter Enders on the occasion of his 70th birthday
Abstract
Bifunctional primary amine thiourea (PAT) organocatalysts show remarkable improvement in enantioselectivity and catalytic activity (turnover frequency) in the asymmetric Michael addition of acetone to β-nitrostyrenes upon dilution. Mechanistic investigations indicate that this behavior corresponds to the inhibition of off-cycle catalyst deactivation at low concentration, rather than to the operation of aggregation phenomena at high concentration. Reaction at low concentration (≤0.2 M in β-nitrostyrene) leads to the minimization of catalyst deactivation and, thus, to the optimization of yield and ee of the Michael addition products.
Key words
primary amine thioureas - Michael addition - asymmetric catalysis - organocatalysis - concentration effectSupporting Information
- Supporting information for this article is available online at http://dx.doi.org/10.1055/s-0036-1589408.
- Supporting Information
-
References
- 1a Tsogoeva SB, Wei SW. Chem. Commun. 2006; 1451
- 1b Yalalov DA, Tsogoeva SB, Schmatz S. Adv. Synth. Catal. 2006; 348: 826
- 2a Huang H, Jacobsen EN. J. Am. Chem. Soc. 2006; 128: 7170
- 2b Lalonde MP, Chen Y, Jacobsen EN. Angew. Chem. Int. Ed. 2006; 45: 6366
- 3a Serdyuk OV, Heckel CM, Tsogoeva SB. Org. Biomol. Chem. 2013; 11: 7051
- 3b Tsakos M, Kokotos CG. Tetrahedron 2013; 69: 10199
- 3c Peng F, Shao Z. J. Mol. Catal. A: Chem. 2008; 285: 1
- 4a Tsakos M, Kokotos CG, Kokotos G. Adv. Synth. Catal. 2012; 354: 740
- 4b Kokotos CG, Kokotos G. Adv. Synth. Catal. 2009; 351: 1355
- 4c Dudzinski K, Pakulska AM, Kwiatkowski P. Org. Lett. 2012; 14: 4222
- 5a John RA. Biochim. Biophys. Acta 1995; 1248: 81
- 5b Maegley KA, Admiraal SJ, Herschlag D. Proc. Natl. Acad. Sci. U.S.A. 1996; 93: 8160
- 5c Jornvall H, Persson B, Krook M, Atrian S, Gonzalez-Duarte R, Jeffery J, Ghosh D. Biochemistry 1995; 34: 6003
- 5d Shuman S, Schwer B. Mol. Microbiol. 1995; 17: 405
- 5e Radominska-Pandya A, Czernik PJ, Little JM, Battaglia E, Mackenzie PI. Drug Metab. Rev. 1999; 31: 817
- 5f Gefflaut T, Blonski C, Perie J, Willson M. Prog. Biophys. Mol. Biol. 1995; 63: 301
- 6 Günler ZI, Companyó X, Alfonso I, Burés J, Jimeno C, Pericàs MA. Chem. Commun. 2016; 52: 6821
- 7a Serra-Pont A, Alfonso I, Jimeno C, Solà J. Chem. Commun. 2015; 51: 17386
- 7b Kasaplar P, Ozkal E, Rodríguez-Escrich C, Pericàs MA. Green Chem. 2015; 17: 3122
- 7c Sagamanova IK, Sayalero S, Martínez-Arranz S, Albéniz AC, Pericàs MA. Catal. Sci. Technol. 2015; 5: 754
- 7d Jimeno C, Cao L, Renaud P. J. Org. Chem. 2016; 81: 1251
- 8 Jimeno C. Org. Biomol. Chem. 2016; 14: 6147
- 9 Zhang X.-J, Liu S.-P, Lao J.-H, Du G.-J, Yan M, Chan AS. C. Tetrahedron: Asymmetry 2009; 20: 1451
- 10 Fuerst DE, Jacobsen EN. J. Am. Chem. Soc. 2005; 127: 8964
- 11a Jang HB, Rho HS, Oh JS, Nam EH, Park SE, Bae HY, Song CE. Org. Biomol. Chem. 2010; 8: 3918
- 11b Lee JW, Ryu TH, Oh JS, Bae HY, Jang HB, Song CE. Chem. Commun. 2009; 7224
- 11c Oh J.-S, Lee J.-W, Ryu TH, Lee JH, Song CE. Org. Biomol. Chem. 2012; 10: 1052
- 11d Oh SH, Rho HS, Lee JW, Lee JE, Youk SH, Chin J, Song CE. Angew. Chem. Int. Ed. 2008; 47: 7872
- 11e Rho HS, Oh SH, Lee JW, Lee JY, Chin J, Song CE. Chem. Commun. 2008; 1208
- 12 Retini M, Bergonzinia G, Melchiorre P. Chem. Commun. 2012; 48: 3336
- 13 Rodríguez-Llansola F, Miravet JF, Escuder B. Chem. Eur. J. 2010; 16: 8480
- 14a Okino T, Hoashi Y, Furukawa T, Xu XN, Takemoto Y. J. Am. Chem. Soc. 2005; 127: 119
- 14b Takemoto Y. Chem. Pharm. Bull. 2010; 58: 593
- 15a Ji Y, Blackmond DG. Catal. Sci. Technol. 2014; 4: 3505
- 15b Burés J, Armstrong A, Blackmond DG. J. Am. Chem. Soc. 2011; 133: 8822
- 16a Barbier V, Couty F, David OR. P. Eur. J. Org. Chem. 2015; 3679
- 16b Berry RW. H, Mazza RJ. Polymer 1973; 14: 172
- 17 Blackmond DG. Angew. Chem. Int. Ed. 2005; 44: 4302
- 18 Simpson AJ, Lam HW. Org. Lett. 2013; 15: 2586
- 19 Morris DJ, Partridge AS, Manville CV, Racys DT, Woodward G, Docherty G, Wills M. Tetrahedron Lett. 2010; 51: 209
- 20 Xue F, Zhang S, Duan W, Wang W. Adv. Synth. Catal. 2008; 350: 2194
- 21 Li P, Wang Y, Liang X, Ye J. Chem. Commun. 2008; 3302
- 22 Gu Q, Guo X.-T, Wu X.-Y. Tetrahedron 2009; 65: 5265
For reviews, see:
For selected examples, see:
For recent examples, see: