Synthesis, structure and antiproliferative activity of chiral polyamines based on a 2-azanorbornane skeleton

Zinc complexes formed by 2,2′-bipyridine and 1,10-phenanthroline moieties combined with 2-azanorbornane: modular chiral catalysts for aldol reactions

“…12 Amine 3 was synthesized from aldehyde 7 in a twostep procedure as recently described. 13 Amine 4 was prepared in an analogous manner from the respective endo aldehyde obtained from alcohol endo-2.…”

“…1 H NMR (500 MHz, CDCl 3 , Me 4 Si) d = 1.04-1.09 (2H, m), 1.27-1.39 (2H, m), 1.30 (3H, d, J = 6.5 Hz), 1.55-1.60 (2H, m), 1.62-1.69 (1H, m), 1.85-1.89 (1H, m), 2.10 (1H, dd, J 1 = 9.0 Hz, J 2 = 2.5 Hz), 2.28 (1H, d, J = 4.0 Hz), 2.58 and 2.72 (2H, ABX, J AB = 13.0 Hz, J AX = 9.0 Hz, J BX = 2.5 Hz), 2.90 (1H, s), 3.59 (1H, q, J = 6.5 Hz), 7.20-7.34 (5H, m). 13 C NMR (125 MHz, CDCl 3 , Me 4 Si) d = 22. 7, 25.2, 29.1, 35.2, 40.7, 48.7, 58.9, 60.3, 70.6, 126.6, 127.4, 128.3, 146.3 (1S,4R,5R,1 0 S)-6.…”

“…1 H NMR: d H (500 MHz; CDCl 3 ; Me 4 Si) 1.13-1.17 (1H, m), 1.34 (3H, d, J = 6.5 Hz), 1.58-1.63 (1H, m), 1.76-1.82 (1H, m), 1.90-1.96 (1H, m), 2.25-2.28 (1H, m), 2.46 (1H, d, J = 10.4 Hz), 2.72 (1H, dd, J 1 = 12.7 Hz, J 2 = 4.0 Hz), 2.97 (1H, d, J = 12.6 Hz), 3.28 (1H, t, J = 5.0 Hz), 3.45 (1H, bs), 3.64 (1H, q, J = 6.5 Hz), 7.20 (1H, t, J = 7.2 Hz), 7.28 (2H, t, J = 7.4 Hz), 7.39 (2H, d, J = 7.3 Hz), 7.67 (1H, dd, J 1 = 8.0 Hz, J 2 = 4.3 Hz), 7.85 and 7.87 (2H, AB q , J = 8.8 Hz), 8.35 and 8.61 (2H, AB q , J = 8.3 Hz), 8.29 (1H, dd, J 1 = 8.1 Hz, J 2 = 1.7 Hz), 8.95 (1H, s, NH), 9.25 (1H, dd, J 1 = 4.3 Hz, J 2 = 1.7 Hz). 13 23.2, 27.9, 32.7, 41.6, 49.7, 57.2, 62.3, 70.3, 120.8, 123.1, 126.5, 127.2; 127.5, 127.7, 128.2, 128.9, 129.3, 136.2, 136.6, 145.7, 146.2, 146.4, 150.6, 155.5, 161.2 23.2, 27.9, 32.7, 41.6, 49.7, 57.2, 62.3, 70.3, 120.7, 123.1, 126.5, 127.2; 127.6, 128.3, 128.6, 128.9, 129.3, 136.2, 136.5, 145.7, 146.2, 150.5, 155.3, 161.…”

Chiral pyrrolidine thioethers and 2-azanorbornane derivatives bearing additional nitrogen functions. Enantiopure ligands for palladium-catalyzed Tsuji-Trost reaction

“…[10][11][12] In our laboratory, it was utilized in the preparation of ligands bearing additional donor atoms (N, S, P, O) and polyamine derivatives exhibiting interesting antiproliferative activity. 10,13,14 In particular, amine 18 based on a 2-azanorbornyl skeleton was obtained from 11 via its conversion into an oxime followed by reduction. 14 In the present work, we decided to extend the family of N,N-donating ligands containing four stereogenic centers by reacting amine 18 with aryl aldehydes leading to the series of imines 19a-19e (Scheme 6).…”

“…10,13,14 In particular, amine 18 based on a 2-azanorbornyl skeleton was obtained from 11 via its conversion into an oxime followed by reduction. 14 In the present work, we decided to extend the family of N,N-donating ligands containing four stereogenic centers by reacting amine 18 with aryl aldehydes leading to the series of imines 19a-19e (Scheme 6). Since these imines were too unstable to be isolated, they were reduced in situ to the corresponding secondary amines with various aryl substituents 20a-20e (85-90% overall yields).…”