POLYVALENT IODINE AND DERIVED CHEMISTRY

乙炔以及所有类型的酯（羧酸酯、磷酸酯、 磺酸盐）是最普遍、最重要和最有价值的 有机化学中的功能和化合物。 两者都发挥着关键作用 机械化学、合成化学和生物有机化学。 最近，我们有 发现并制备了新型功能化乙炔， 炔基碘鎓盐，以及迄今为止未知的炔基酯。 我们将利用这一激动人心的发展并以此为基础 详细阐述化学以及药物和生物化学 我们的新炔基碘物种和炔基酯。 具体来说，我们 应研究： a) 两者的电环加成 炔基碘鎓类和炔基酯； b) 炔基化和 亲电乙炔化学，c) 通过 RC 的炔基氨基酸（三重 键）CIPhOTf； d) 甲硅烷氧基乙炔和炔醇化物化学； e) 共轭 通过 RC（三键）CIPhOTf 偶联形成烯炔； f) P-叶立德；克) 乙烯基碘鎓种类。 我们将继续检查其药用和生化特性以及 这些化合物的重要性。 炔基碘鎓盐和鏻盐 将通过“炔基化”被评估为潜在的新抗肿瘤药物 生物亲核试剂。 现有数据表明，一些成员 该家族的成员对小鼠白血病细胞 (L1210) 有活性 人 T 淋巴细胞 (Molt-4F) 以及人 T 淋巴细胞 (MT-4) 细胞。 炔基羧酸酯和磷酸酯将被检查为 基于机制的蛋白酶和磷酸酶抑制剂（“自杀 基材”）。 初步结果表明CH3C(三键)COC(O)Ar 是丝氨酸蛋白酶的有效抑制剂。 类似地，n-BuC(三 键)COP(O)(OEt)2 和相关的炔基磷酸酯是有效的 细菌三酯磷酸酶抑制剂。 这个项目对两种相对较新的类型进行基础研究—— 化合物类别，即炔基碘鎓盐和炔基酯， 对合成、物理有机、医药有重大影响，如 以及生物有机化学。

Acetylenes as well as Esters of all types (carboxylate, phosphate, sulfonate) are among the most ubiquitous, important and valuable functionalities and compounds in organic chemistry. Both play key roles in mechanistic, synthetic and bioorganic chemistry. Recently, we have discovered and prepared novel types of functionalized acetylenes, alkynyliodonium salts, as well as the hitherto unknown alkynyl esters. We shall capitalize and build upon this exciting development by elaborating the chemistry, as well as the medicinal and biochemistry of our new alkynyliodonium species and alkynyl esters. Specifically, we shall investigate: a) electrocyclic cycloadditions of both alkynyliodonium species and alkynyl esters; b) alkynylations and electrophilic acetylene chemistry, c) alkynyl amino acids via RC (triple bond) CIPhOTf; d) siloxyacetylene and ynolate chemistry; e) conjugated enyne formation via coupling of RC(triple bond)CIPhOTf; f) P-ylides; g) vinyliodonium species. We shall continue to examine the medicinal and biochemical,properties and significance of these compounds. Alkynyliodonium and phosphonium salts will be evaluated as potential new antitumor agents via "alkynylation" of biological nucleophiles. Data already in hand indicate that some members of this family are active against murine leukemia cells (L1210) and human-T-lymphoblast cells (Molt-4F) as well as the human-T-lymphocyte (MT-4) cells. Alkynyl carboxylates and phosphates will be examined as mechanism based protease and phosphatase inhibitors ("suicide substrates"). Preliminary results show that CH3C(triple bond)COC(O)Ar are potent inhibitors of serine based proteases. Similarly, n-BuC(triple bond)COP(O)(OEt)2 and related alkynyl phosphate esters are potent inhibitors of a bacterial triester phosphatase. This program of fundamental research on two relatively new types-and classes of compounds, namely alkynyliodonium salts and alkynyl esters, has major implications for synthetic, physical-organic, medicinal, as well as bioorganic chemistry.