Nájera Carmen, Sansano José M
Department of Organic Chemistry and Centro de Innovación, en Química Avanzada (ORFEO-CINQA)Faculty of Sciences, University of Alicante, 03080, Alicante, Spain.
Department of Organic Chemistry, Instituto de Síntesis Orgánica, and Centro de Innovación en Química Avanzada (ORFEO-CINQA)Faculty of Sciences, University of Alicante, 03080, Alicante (Spain).
Chem Rec. 2016 Dec;16(6):2430-2448. doi: 10.1002/tcr.201500283. Epub 2016 Apr 5.
2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl (binap) and phosphoramidites are privileged chiral ligands that have been tested in the coinage-metal-catalyzed 1,3-dipolar cycloadditions of metalloazomethine ylides and electrophilic alkenes. Silver(I), copper(II), and gold(I) salts have been evaluated in all of these reactions. Maleimides, acrylates, fumarates, 1,2-bis(phenylsulfonyl)ethylene, and enones reacted with imino esters to give the corresponding endo-prolinates, such as hepatitis C (HCV) inhibitors, in high diastereo- and enantioselectivity using either binap-silver and -gold(I) or phosphoramidite-silver complexes. In the case of nitroalkenes, exo-4-nitroprolinates were obtained using silver or copper(II) phosphoramidite complexes. Azlactones reacted with maleimides and acrylates to give pyrrolines only in the presence of binap-gold(I) complexes. The observed enantioselectivity and mechanism of these 1,3-dipolar cycloadditions were studied for the most relevant examples by means of DFT calculations.
2,2'-双（二苯基膦基）-1,1'-联萘（联萘二膦）和亚磷酰胺酯是重要的手性配体，已在金属偶氮甲碱叶立德和亲电烯烃的铸币金属催化的1,3-偶极环加成反应中进行了测试。在所有这些反应中都评估了银（I）、铜（II）和金（I）盐。马来酰亚胺、丙烯酸酯、富马酸酯、1,2-双（苯基磺酰基）乙烯和烯酮与亚氨基酯反应，使用联萘二膦-银和-金（I）或亚磷酰胺酯-银配合物，以高非对映选择性和对映选择性得到相应的内型脯氨酸酯，如丙型肝炎（HCV）抑制剂。对于硝基烯烃，使用银或铜（II）亚磷酰胺酯配合物可得到外型4-硝基脯氨酸酯。只有在联萘二膦-金（I）配合物存在下，恶唑酮与马来酰亚胺和丙烯酸酯反应才能得到吡咯啉。通过密度泛函理论计算，对这些1,3-偶极环加成反应中最相关的例子的对映选择性和反应机理进行了研究。
