SYNTHETIC APPLICATIONS OF ALLENES IN ORGANIC CHEMISTRY

异氰酸酯、卡宾和硝烯与异氰酸酯的环加成反应 取代的烯丙基硫化物将用于生成 α-亚烷基-β-内酰胺、亚甲基环丙烷和 分别为亚甲基氮杂环丙烷。β-内酰胺类药物将用于制备 基于机理的单环β-内酰胺酶抑制剂。亚烷基 功能性将在稳定最初的酰基酶方面起到关键作用。 中级的。α-亚乙烯(即外环烯丙基)β-内酰胺类药物 也要准备和测试(β-内酰胺酶抑制活性)作为 他们的NU-磺酸盐衍生物。高度应变的亚甲基环丙烷和 亚甲基氮杂环丙烷将通过分子内加成生成 卡宾和硝烯对选定的联烯。预期中的 由此生产的三亚甲基甲基乙烷类中间体将 分子内捕获产生有用的双环和三环体系。 通过2，3-Sigmatrotic合成手性烯基亚硫醚 易得的手性丙叉醇的重排。这些 将利用这些材料制备手性β-内酰胺类药物，并探索 烯丙基阴离子的构型稳定性。

The cycloaddition reactions of isocyanates, carbenes, and nitrenes with substituted allenyl sulfides will be used to generate Alpha-alkylidene-Beta-lactams, methylenecyclopropanes, and methyleneaziridines respectively. The Beta-lactams will be used to prepare mechanism-based monocyclic Beta-lactamase inhibitors. The alkylidene functionality will serve a key role in stabilizing the initial acyl-enzyme intermediate. Alpha-Vinylidene (i.e. exocyclic allenyl) Beta-lactams will also be preapared and tested (for Beta-lactamase inhibitory activity) as their Nu-sulfonate derivatives. Highly strained methylenecyclopropanes and methyleneaziridines will be generated via the intramolecular addition of carbenes and nitrenes to selected allenes. The expected trimethylenemethane-type intermediates thereby produced will be intramolecularly trapped generating useful bi- and tricyclic systems. Chiral allenyl sulfoxides will be prepared via 2,3-sigmatropic rearrangement of the readily available chiral propargylic alcohols. These materials will be used to prepare chiral Beta-lactams and to explore the configurational stability of allenyl anions.