Synthesis 2015; 47(07): 934-943
DOI: 10.1055/s-0034-1380158
psp
© Georg Thieme Verlag Stuttgart · New York

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

Luis M. Castelló
a  Departamento 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
a  Departamento 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*
a  Departamento 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
b  Departmento 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
b  Departmento 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
c  IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain   Email: [email protected]
,
Fernando P. Cossío
b  Departmento 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
c  IKERBASQUE, Basque Foundation for Science, 48011 Bilbao, Spain   Email: [email protected]
› Author Affiliations
Further Information

Publication History

Received: 14 January 2015

Accepted: 16 January 2015

Publication Date:
19 February 2015 (online)


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.

 
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