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.
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收藏
页码：3861 / 3870
页数：10
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