Synthesis and Applications of Asymmetric Catalysis Using Chiral Ligands Containing Quinoline Motifs

Abstract

In the past decade, asymmetric synthesis of chiral ligands containing quinoline motifs, a family of natural products displaying a broad range of structural diversity and their metal complexes have become the most significant methodology for the generation of enantiomerically pure compounds of biological and pharmaceutical interest. This review provides comprehensive insight on the plethora of nitrogen-based chiral ligands containing quinoline motifs and organocatalysts used in asymmetric synthesis. However, it is circumscribed to the synthesis of quinoline-based chiral ligands and metal complexes, and their applications in asymmetric synthesis as a homogeneous and heterogeneous catalyst.

Enantioselective 1,3-Dipolar Cycloaddition Using (Z)-α-Amidonitroalkenes as a Key Step to the Access to Chiral cis-3,4-Diaminopyrrolidines

“…1 H NMR (300 MHz, CDCl 3 ): δ = 1.95 (s, 3H, CH 3 ), 3.71 (s, 3H, OCH 3 ), 4.53 (d, J = 7.2 Hz, 1H, NHCHCOOMe), 4.92 (d, J = 7.3 Hz, 1H, NHCHPh), 5.08 (dd, J = 7.3, 5.1 Hz, 1H, NO 2 CH), 5.33 (ddd, J = 8.5, 7.2, 5.0 Hz, 1H, NHCHCHNO 2 ), 6.72 (d, J = 8.8 Hz, 1H, NHCOCH 3 ), 7.47-7.54 (m, 2H, ArH), 7.57 (dd, J = 8.5, 1.8 Hz, ArH), 7.80-7.94 (m, 4H, ArH). 13 (33), 220 (25), 219 (18), 209 (25), 208 (11), 196 (21), 193 (24), 182 (30), 180 (44), 168 (25), 167 (82), 166 (29), 165 (100), 153 (14), 152 (26), 140 (14), 43 (32). HRMS (DIP) calculated for 13 C NMR (101 MHz, CDCl 3 ): δ =21.3 (CH 3 ), 22.9 (CH 3 ), 53.0 (NHCHCO), 55.7 (OCH 3 ), 61.9 (CNHCO), 65.2 (PhCHNH), 93.8 (CNO 2 ), 127.3, 130.0, 139.6 (ArC), 169.1, 171.1 (2xC=O).…”

“…HRMS (DIP) calculated for 13 C NMR (101 MHz, CDCl 3 ): δ =21.3 (CH 3 ), 22.9 (CH 3 ), 53.0 (NHCHCO), 55.7 (OCH 3 ), 61.9 (CNHCO), 65.2 (PhCHNH), 93.8 (CNO 2 ), 127.3, 130.0, 139.6 (ArC), 169.1, 171.1 (2xC=O). MS (EI) m/z: 275 (M + -NO 2 , 4%), 217 (10), 216 (53), 215 (100), 191 (32), 189 (13), 188 (84), 184 (24), 183 (18), 174 (12), 173 (35), 172 (11), 159 (12), 157 (27), 156 (64), 149 (17), 146 (64), 144 (26), 132 (14), 131 (82), 130 (36), 129 (58), 128 (12), 115 (22), 91 (20), 57 (14) 19 F NMR (300 MHz, CDCl 3 ): δ =−115.37 ppm. 13 C NMR (101 MHz, CDCl 3 ): (CH 3 ), 53.3 (NHCHCO), 55.1 (OCH 3 ), 61.9 (CNHCO), 64.0 (PhCHNH), 92.8 (CNO 2 ), 116.3, 116.6, 130.1, 130.2, 162.4, 164.9 (ArC), 167.…”

“…8, 171.8 (2xC=O). MS (EI) m/z: 279 (M + -NO 2 , 4%), 277 (13), 220 (38), 219 (98), 195 (24), 192 (90), 188 (16), 187 (13), 178 (15), 177 (48), 176 (14), 175 (12), 161 (26), 160 (55), 150 (100), 148 (31), 135 (75), 133 (37), 108 (16), 101 (15), 43 (60). HRMS (DIP) calculated for C 14 H 16 FN 3 O 5 : 325.1074; found: 325.1076.…”

“…It is well known that the enantioselective 1,3-dipolar cycloaddition (1,3-DC) of fleeting azomethine ylides and alkenes rapidly gives access to pyrrolidines, with excellent results [ 24 , 25 , 26 , 27 , 28 ]. In this line, the selection of the appropriate dipolarophile can result in multiple functionalities at the 3- and 4-carbon atoms of this heterocycle.…”

Functionalization of Pyridine and Quinoline Scaffolds by Using Organometallic Li‐, Mg‐ and Zn‐Reagents

“…Many substituted pyridines and quinoline derivatives play a big part in biological activity, drugs, catalysis and material science [1–30] . Given the significance of these nitrogen‐based heterocyclic cores, especially pyridine/quinoline, which are chiral ligands or catalysts in the majority of the synthesis of chiral organic intermediates, the regio‐ and stereoselective functionalization of heterocycles is a significant synthetic challenge [31–40] . The use of organolithium, ‐magnesium and ‐zinc organometallics for achieving regioselective metalation has been demonstrated by Knochel, Snieckus, Schlosser, Quéginer and Mongin as well as Gros, etc.…”