Halocyclization and Palladium(II)-Catalyzed Amidocarbonylation of Unsaturated Aminopolypols. Synthesis of 1,4-Iminoglycitols as Potential Glycosidase Inhibitors

Synthesis of Functionalized Heterocycles via Oxidative Carbonylation

“…In the presence of Pd Scheme 21 Oxidative carbonylation of propargyl amines with carbon dioxide and carbon monoxide (II) and indium(III) triflate, α-pyrrolidinyl ketones were obtained in moderate to good yields with CuCl 2 as oxidant and chlorine source [83]. This methodology was applied to the total synthesis of (AE)-ferruginine, (AE)-anatoxin-a, and 1,4-iminoglycitols [84][85][86].…”

Palladium-catalysed reactions of alcohols. Part B: Formation of C–C and C–N bonds from unsaturated alcohols

“…[220][221][222] This intramolecular aminocarbonylation procedure was selective, even from unsaturated aminopolyols (Eq. 127), 223,224 and was extended to N-protected 4-hydroxy-5-hexenylamines. 222,225 Scheme 23.…”

Aminohydroxylation of divinylcarbinol and its application to the synthesis of bicyclic hydroxypyrrolidine and aminotetrahydrofuran building blocks

“…Firstly, the silyl-protecting group was removed by acidic hydrolysis with Dowex H + in methanol and the unprotected aminodiols anti-V, syn-V, and anti-III were subjected to the second crucial step of the syntheses. The domino Pd(II)-cyclisation/oxycarbonylation reaction was carried out under standard reaction conditions (Gracza et al, 1991;Hümmer et al, 1997) affording bicyclic lac- 3419,3350,3066,3034,2952,2927,2856,1700,1518,1471,1462,1251,1080,835,776,696 3429, 3344, 2952, 2927, 2856, 1692, 1516, 1471, 1462, 1251, 1077, 1027, 835, 775, 3307, 2952, 1779, 1694, 1531, 1417, 1246, 1187, 1147, 1082, 1070, 976, 900, 839, 738, 3506, 3275, 2927, 2856, 1599, 1462, 1404, 1327, 1252, 1158, 1090, 835, 777, 664, 3494, 3275, 2954, 2927, 2856, 1599, 1495, 1471, 1402, 1324, 1252, 1157, 1090, 835, 777, 662, 3510, 3284, 2953, 2928, 2885, 2856, 1598, 1471, 1404, 1327, 1252, 1158, 1089, 835, 813, 778, 665, 3444, 3276, 2992, 2873, 1597, 1495, 1427, 1402, 1319, 1152, 1089, 813, 660, 3423,3271,2924,1714,1599,1427,1402,1320,1306,1152,1089,1034,929,813,662,547 1 H NMR (300 MHz, CD 3 OD), δ: 2.42 (s, 3H, CH 3 in Ts), 3.21 (ddd, 1H, J 1A,2 = 5.1 Hz, J 1B,2 = 5.1 Hz, J 2,3 = 5.9 Hz, H-2), 3.43 (dd, 1H, J 1A,2 = 5.1 Hz, J 1A,1B = 11.3 Hz, H-1A), 3.57 (dd, 1H, J 1B,2 = 5.0 Hz, J 1A,1B = 11.3 Hz, H-1B), 4.08 (tt, 1H, J 3,5A = 1.5 Hz, J 3,5B = 1.5 Hz, J 2,3 = 5.9 Hz, J 3,4 = 5.9 Hz, H-3), 5.05 (dt, 1H, J 3,5A = 1.5 Hz, J 5A,5B = 1. 3483, 2920, 1782, 1598, 1456, 1401, 1337, 1155, 1089, 1042, 813, 656, 588, 3421, 2889, 1756, 1599, 149...…”

“…The configuration of pyrrolidinolactones l-arabino-IXa, -IXb and l-xyloIXa, -IXb was established by comparing the 1 H NMR data and specific rotation with the literature data of N-benzyloxycarbonyl-2,3,6-trideoxy-3,6-imino-d-arabino-1,4-hexonolactone (Jäger & Hüm-mer, 1990;Hümmer et al, 1997;[α] 22 D -71.6 • (c = 0.666, CHCl 3 )). These pyrrolidinolactones serve as precursors for syntheses of hydroxypyrrolidines (1,4-iminoglycitols) known to show high activity against glycosidases (Fleet et al, 1985;Bashyal et al, 1987;Winkler & Holan, 1989).…”

“…Previous investigations in our laboratory have demonstrated that the Pd(II)-catalysed oxy-and amidocarbonylation of unsaturated polyols and amino polyols represent an efficient entry to cis-fused 5-membered bicyclic lactones (Gracza et al, 1991;Jäger et al, 1997;Hümmer et al, 1997). This methodology has been used as the key step in a number of natural product syntheses (Gracza & Jäger, 1992, 1994Dixon et al, 1999;Babjak et al, 2002Babjak et al, , 2005Karlubíková et al, 2011).…”