Synthesis of some optically active terpenoid-derived thioamides

<p>Several terpenoid-derived thioamides have been synthesized in the reactions taking advantage of the electrophilicity of the carbonyl function in terpenones and the nucleophilicity of the terpenone lithium enolates. The optically active β-hydroxythioamide derivatives <b>4, 6, 8, 10, 12</b> have been obtained by reacting the thioacetanilide dianion <b>2</b> with terpenones. The reaction of the enolate anions of (-)-menthone and (1R)-(+)-camphor with phenyl isothiocyanate gave rise to the formation of the corresponding β-ketothioamides <b>13</b>, <b>14</b>. In a multicomponent reaction (MCRs) with benzylamine and formaldehyde, <b>14</b> yielded the spirohexahydropyrimidine <b>15</b>.</p

Synthesis of Polycyclic δ‑Lactams with Bridged Benzomorphan Skeleton: Selectivity and Diversity Driven by Substituents

An efficient synthesis of bromofunctionalized 2,6-methano- and 1,5-methano-benzomorphanones, starting from easily available 6-benzyl-3,6-dihydropyridin-2­(1<i>H</i>)-ones, is described. Furthermore, the synthesis of bridged benzomorphanones with hitherto not known polycyclic systems containing 2- or 3-azabicyclo[4.1.0]­heptane units is developed upon treatment of both 2,6- and 1,5-methanobromobenzomorphans with <i>t-</i>BuOK. The effects of substituents on the diversity and stereoselectivity of both transformations are studied