Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Luis M. Castelló; Carmen Nájera; José M. Sansano; Olatz Larrañaga; Abel de Cózar; Fernando P. Cossío

doi:10.1055/s-0034-1380158

Synthesis, Inhaltsverzeichnis

Synthesis 2015; 47(07): 934-943
DOI: 10.1055/s-0034-1380158

psp

Enantioselective Synthesis of exo-4-Nitroprolinates from Nitroalkenes and Azomethine Ylides Catalyzed by Chiral Phosphoramidite·Silver(I) or Copper(II) Complexes

Luis M. Castelló

^aDepartamento de Química Orgánica, Instituto de Síntesis Orgánica (ISO), and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Alicante, Apdo. 99, 03080-Alicante, Spain

,

Carmen Nájera

^aDepartamento de Química Orgánica, Instituto de Síntesis Orgánica (ISO), and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Alicante, Apdo. 99, 03080-Alicante, Spain

,

José M. Sansano*

^aDepartamento de Química Orgánica, Instituto de Síntesis Orgánica (ISO), and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Universidad de Alicante, Apdo. 99, 03080-Alicante, Spain

,

Olatz Larrañaga

^bDepartmento de Química Orgánica I, Facultad de Química, and Centro de Innovación en Química Avanzada (ORFEO CINQA), Universidad del País Vasco, P. K. 1072, 20018 San Sebastián, Spain

,

Abel de Cózar

^bDepartmento de Química Orgánica I, Facultad de Química, and Centro de Innovación en Química Avanzada (ORFEO CINQA), Universidad del País Vasco, P. K. 1072, 20018 San Sebastián, Spain

^cIKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain eMail: jmsansano@ua.es

,

Fernando P. Cossío

^bDepartmento de Química Orgánica I, Facultad de Química, and Centro de Innovación en Química Avanzada (ORFEO CINQA), Universidad del País Vasco, P. K. 1072, 20018 San Sebastián, Spain

^cIKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain eMail: jmsansano@ua.es

› Institutsangaben

Abstract

Alle Artikel dieser Rubrik

Abstract

Chiral complexes formed by privileged phosphoramidites derived from chiral binol and optically pure Davies’ amines, and copper(II) triflate, silver(I) triflate or silver(I) benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between nitroalkenes and azomethine ylides generated from α-amino acid derived imino esters. These three methods can be conducted at room temperature to afford the exo-cycloadducts (4,5-trans-2,5-cis-4-nitroprolinates) with high diastereoselectivity and high enantioselectivity. In general, the three procedures are complementary but silver catalysts are more versatile and less sensitive to sterically congested starting materials.

Key words

dipolar cycloaddition - asymmetric catalysis - azomethine ylides - phosphoramidite - copper - silver

Volltext

Referenzen

References

For general reviews dealing with general 1,3-DC, see:

1a Synthetic Applications of 1,3-Dipolar Cycloaddition Chemistry Towards Heterocycles and Natural Products. Padwa A, Pearson WH. John Wiley & Sons; New Jersey: 2003
1b Nájera C, Sansano JM. Curr. Org. Chem. 2003; 7: 1105
1c Eberbach W In Science of Synthesis . Vol. 27. Padwa A. Georg Thieme Verlag; Stuttgart: 2004: 441
1d Coldham I, Hufton R. Chem. Rev. 2005; 105: 2765
1e Nair V, Suja TD. Tetrahedron 2007; 63: 12247
1f Padwa A, Bur SK. Tetrahedron 2007; 63: 5341
1g Kanemasa S. Heterocycles 2010; 82: 87
1h Han M.-Y, Jia J.-Y, Wang W. Tetrahedron Lett. 2014; 55: 784

2 Nájera C, Sansano JM. Curr. Top. Med. Chem. 2014; 14: 1271

3a Zubia A, Mendoza L, Vivanco S, Aldaba E, Carrascal T, Lecea B, Arrieta A, Zimmerman T, Vidal-Vanaclocha F, Cossío FP. Angew. Chem. Int. Ed. 2005; 44: 2903
3b San Sebastián E, Zimmerman T, Zubia A, Vara Y, Martín E, Sirockin F, Dejaegere A, Stote RH, López X, Pantoja-Uceda D, Valcárcel M, Mendoza L, Vidal-Vanaclocha F, Cossío FP, Blanco FJ. J. Med. Chem. 2013; 56: 735

4 Tripathi RP, Bisht SS, Pandey VP, Pandey SK, Singh S, Sinha SK, Chatuvedi V. Med. Chem. Res. 2011; 20: 1515
5 Conde E, Bello D, de Cózar A, Sánchez M, Vázquez MA, Cossío FP. Chem. Sci. 2012; 3: 1486

For recent reviews of asymmetric 1,3-DC, see:

6a Pellissier H. Tetrahedron 2007; 63: 3235
6b Nájera C, Sansano JM. Top. Heterocycl. Chem. 2008; 12: 117
6c Stanley LM, Sibi MP. Chem. Rev. 2008; 108: 2887
6d Álvarez-Corral M, Muñoz-Dorado M, Rodríguez-García I. Chem. Rev. 2008; 108: 3174
6e Naodovic M, Yamamoto H. Chem. Rev. 2008; 108: 3132
6f Nájera C, Sansano JM, Yus M. J. Braz. Chem. Soc. 2010; 21: 377
6g Kissane M, Maguire AR. Chem. Soc. Rev. 2010; 39: 845
6h Adrio J, Carretero JC. Chem. Commun. 2011; 47: 6784
6i Adrio J, Carretero JC. Chem. Commun. 2014; 50: 12434

7 The exo descriptor refers the approach of the dipolarophile in which the electron-withdrawing group of the 1,3-dipole and the nitro group are orientated in the opposite direction.
8 Arai T, Mishiro A, Yokoyama N, Suzuki K, Sato H. J. Am. Chem. Soc. 2010; 132: 5338
9 Yan X.-X, Peng Q, Zhang Y, Hong W, Hou X.-L, Wu Y.-D. Angew. Chem. Int. Ed. 2006; 45: 1979
10 Grigg R, Kilner C, Sarker MA. B, Orgaz de la Cierva C, Dondas HA. Tetrahedron 2008; 64: 8974

Silver-catalyzed processes have been attempted, but these resulted in low diastereoselectivities and moderate to low, see:

11a Shimizu K, Ogata K, Fukuzawa S.-I. Tetrahedron Lett. 2010; 51: 5068
11b Gu X, Xu Z.-J, Lo VK.-Y, Che C.-M. Synthesis 2012; 44: 3307

12 Imae K, Konno T, Ogata K, Fukuzawa S.-I. Org. Lett. 2012; 14: 4410
13 Teichert JF, Feringa BL. Angew. Chem. Int. Ed. 2010; 49: 2486

Phosphoramidite ligands 1 are considered as a family of second-generation privileged ligands:

14a ChemFiles, 2006, 6, issue 8; http://www.sigmaaldrich.com.
14b Privileged Chiral Ligands and Catalysts . Zhou Q.-L. Wiley-VCH; Weinheim: 2011

15 For an account, see: Nájera C, Sansano JM. J. Organomet. Chem. 2014; 771: 78

16a Castelló LM, Nájera C, Sansano JM, Larrañaga O, de Cózar A, Cossío FP. Org. Lett. 2013; 15: 2902
16b Lautens M, Zhang L. Synfacts 2013; 9: 0985

17 Castelló LM, Nájera C, Sansano JM, Larrañaga O, de Cózar A, Cossío FP. Adv. Synth. Catal. 2014; 356: 3861

18a Nájera C, Retamosa MG, Sansano JM. Angew. Chem. Int. Ed. 2008; 47: 6055
18b Nájera C, Retamosa MG, Rodríguez M, Sansano JM, de Cózar A, Cossío FP. Eur. J. Org. Chem. 2009; 15: 5622

19 de Cózar, A.; private communication.

Enantioselective Synthesis of exo-4-Nitroprolinates from Nitro­alkenes and Azomethine Ylides Catalyzed by Chiral Phosphor­amidite·Silver(I) or Copper(II) Complexes

Enantioselective Synthesis of exo-4-Nitroprolinates from Nitroalkenes and Azomethine Ylides Catalyzed by Chiral Phosphoramidite·Silver(I) or Copper(II) Complexes