A concise total synthesis of (+)-deoxocassine and (−)-deoxoprosophylline from d-xylose

Cutting-Edge and Time-Honored Strategies for Stereoselective Construction of C–N Bonds in Total Synthesis

“…Carbon–nitrogen bonds in several relatively simple 2-substituted piperidine natural products, specifically (−)-andrachcinidine, (+)-β-conhydrine, (+)-deoxocassine, (+)-perhydro-8-indolizidinol, and (−)-deoxoprosophylline were established by the reaction of different linear sulfonate precursors with sodium azide. In this series, the total synthesis of (−)-epiquinamide A, a nicotinic agonist in central nervous system (CNS) disorders, examplifies the stereoselective installation of both C–N bonds of the alkaloid using the azidolysis strategy (Scheme ).…”

“…Similar amination reactions by nucleophilic substitution with sodium azide in fiveor sixmembered ring systems were utilized for the syntheses of (+)-nangustine, 190 (+)-febrifugine, 191 pachastrissamine (jaspine B), 192 dysiherbaine, 193 spicamycin, 194 and antitumor agent FR901464. 195 Carbon−nitrogen bonds in several relatively simple 2-substituted piperidine natural products, specifically (−)andrachcinidine, 196 (+)-β-conhydrine, 197 (+)-deoxocassine, 199 (+)-perhydro-8-indolizidinol, 198 and (−)-deoxoprosophylline 199 were established by the reaction of different linear sulfonate precursors with sodium azide. In this series, the total synthesis of (−)-epiquinamide A, a nicotinic agonist in central nervous system (CNS) disorders, examplifies the stereoselective installation of both C−N bonds of the alkaloid using the azidolysis strategy (Scheme 41).…”

A short and efficient formal synthesis of (R)-pipecolic acid from the ring expansion of chiral aziridine

“…Piperidines are the key structural features present in several biologically active natural products especially alkaloids such as fagomine (8) an glycosidase inhibitors [22,23], febrifugine (9) [24,25], tetrazomine (10) [26], sedamine (11) [27], swainsonine (12) [11], pipecolic acid (13) [11], isosolenopsin (14) [20,[28][29][30][31], deoxocassine (15) [20,[32][33][34][35] and spectaline (16) [36,37].…”

A Concise Synthesis of (2R,3R)‐ and (2R,3S)‐3‐Hydroxypipecolic Acids, and Total Synthesis of (–)‐Deoxoprosopinine and (+)‐2‐epi‐Deoxoprosopinine from D‐Glycals

“…Later, a very efficient asymmetric synthesis of (+)‐deoxoprosopinine was presented by Comins and coworkers in 2001 12b. More recently, a synthesis of (–)‐deoxoprosophylline 6 was reported13 starting from D ‐xylose, and using a Wittig reaction as a key step. There are several other reports in the literature of the synthesis of these molecules from chiral building blocks 14…”