Efficient Diastereo- and Enantioselective Synthesis of exo-Nitroprolinates by 1,3-Dipolar Cycloadditions Catalyzed by Chiral Phosphoramidite.Silver(I) Complexes

被引：27
|
作者：
Castello, Luis M. [1 ,2 ,5 ]
Najera, Carmen [1 ,2 ,5 ]
Sansano, Jose M. [1 ,2 ,5 ]
Larranaga, Olatz [3 ,5 ]
de Cozar, Abel [3 ,4 ,5 ]
Cossio, Fernando P. [3 ,4 ,5 ]
机构：
[1] Univ Alicante, ISO, Dept Quim Organ, E-03080 Alicante, Spain
[2] Univ Alicante, Ctr Innovac Quim Avanzada ORFEO CINQA, E-03080 Alicante, Spain
[3] Univ Basque Country, Fac Quim, Dept Quim Organ 1, E-20018 San Sebastian, Spain
[4] Basque Fdn Sci, Ikerbasque, E-48011 Bilbao, Spain
[5] Ctr Innovac Quim Avanzada ORFEO CINQA, Catalonia, Spain
来源：
ADVANCED SYNTHESIS & CATALYSIS | 2014年 / 356卷 / 18期
关键词：
asymmetric synthesis; azomethine ylides; dipolar cycloaddition; phosphoramidites; silver; ASYMMETRIC 3+2 CYCLOADDITION; AZOMETHINE YLIDES; CONJUGATE ADDITION; NITROALKENES; INHIBITORS; IMINOESTERS; ESTERS;
D O I：
10.1002/adsc.201400563
中图分类号：
O69 [应用化学];
学科分类号：
081704 ;
摘要：
Chiral complexes formed by privileged phosphoramidites and silver triflate or silver benzoate are excellent catalysts for the general 1,3-dipolar cycloaddition between azomethine ylides generated from alpha-amino acid-derived imino esters and nitroalkenes affording with high dr the exo-cycloadducts 4,5-trans-2,5-cis-4-nitroprolinates in high ee at room temperature. In general, better results are obtained using silver rather than copper(II) complexes. In many cases the exo-cycloadducts can be obtained in enantiomerically pure form just after simple recrystallization. The mechanism and the justification of the experimentally observed stereodiscrimination of the process are supported by DFT calculations. These enantiomerically enriched exo-nitroprolinates can be used as reagents for the synthesis of nitropiperidines, by ester reduction and ring expansion, which are inhibitors of farnesyltransferase.
引用
收藏
页码：3861 / 3870
页数：10
相关论文
共 47 条
  • [1] Synthesis of Prolines by Enantioselective 1,3-Dipolar Cycloaddition of Azomethine Ylides and Alkenes Catalyzed by Chiral Phosphoramidite-Silver(I) Complexes
    Najera, Carmen
    de Gracia Retamosa, Maria
    Martin-Rodriguez, Maria
    Sansano, Jose M.
    de Cozar, Abel
    Cossio, Fernando P.
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2009, 2009 (32) : 5622 - 5634
  • [2] Gold(I)-Catalyzed Diastereo- and Enantioselective 1,3-Dipolar Cycloaddition and Mannich Reactions of Azlactones
    Melhado, Asa D.
    Amarante, Giovanni W.
    Wang, Z. Jane
    Luparia, Marco
    Toste, F. Dean
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (10) : 3517 - 3527
  • [3] Enantioselective Synthesis of exo-4-Nitroprolinates from Nitroalkenes and Azomethine Ylides Catalyzed by Chiral Phosphoramidite•Silver(I) or Copper(II) Complexes
    Castello, Luis M.
    Najera, Carmen
    Sansano, Jose M.
    Larranaga, Olatz
    de Cozar, Abel
    Cossio, Fernando P.
    SYNTHESIS-STUTTGART, 2015, 47 (07): : 934 - 943
  • [4] Diastereo- and Enantioselective Synthesis of Fluorinated Proline Derivatives via Copper(I)-Catalyzed Asymmetric 1,3-Dipolar Cycloaddition
    Li, Qing
    Ding, Chang-Hua
    Li, Xiao-Hui
    Weissensteiner, Walter
    Hou, Xue-Long
    SYNTHESIS-STUTTGART, 2012, 44 (02): : 265 - 271
  • [5] Catalytic asymmetric homo-1,3-dipolar cycloadditions of azomethine ylides: diastereo- and enantioselective synthesis of imidazolidines
    Zhu, Ren-Yi
    Wang, Cong-Shuai
    Jiang, Fei
    Shi, Feng
    Tu, Shu-Jiang
    TETRAHEDRON-ASYMMETRY, 2014, 25 (08) : 617 - 624
  • [6] Enantioselective synthesis of polysubstituted prolines by Binap-silver-catalyzed 1,3-dipolar cycloadditions
    Najera, Carmen
    Retamosa, M. de Gracia
    Sansano, Jose M.
    de Cozar, Abel
    Cossio, Fernando P.
    TETRAHEDRON-ASYMMETRY, 2008, 19 (24) : 2913 - 2923
  • [7] 1,3-dipolar cycloadditions of azomethine ylides with chiral acrylates derived from methyl (S)- and (R)-lactate:: diastereo- and enantioselective synthesis of polysubstituted prolines
    Najera, Carmen
    Retamosa, M. de Gracia
    Sansano, Jose M.
    TETRAHEDRON-ASYMMETRY, 2006, 17 (13) : 1985 - 1989
  • [8] An efficient approach to chiral fullerene derivatives by catalytic enantioselective 1,3-dipolar cycloadditions
    Filippone S.
    Maroto E.E.
    Martín-Domenech Á.
    Suarez M.
    Martín N.
    Nature Chemistry, 2009, 1 (7) : 578 - 582
  • [9] An efficient approach to chiral fullerene derivatives by catalytic enantioselective 1,3-dipolar cycloadditions
    Filippone, Salvatore
    Maroto, Enrique E.
    Martin-Domenech, Angel
    Suarez, Margarita
    Martin, Nazario
    NATURE CHEMISTRY, 2009, 1 (07) : 578 - 582
  • [10] Diastereo- and Enantioselective Construction of 3,3′-Pyrrolidinyldispirooxindole Framework via Catalytic Asymmetric 1,3-Dipolar Cycloadditions
    Dai, Wei
    Jiang, Xiao-Li
    Wu, Qiong
    Shi, Feng
    Tu, Shu-Jiang
    JOURNAL OF ORGANIC CHEMISTRY, 2015, 80 (11): : 5737 - 5744
12345