CHIRAL APPROACHES TO NATURAL PRODUCT SYNTHESIS

该研究涉及到许多新的C-C和C-N键的开发 形成最终应用于全合成的反应， 重要材料，特别是： a）将各种烯丙基锡试剂立体控制地添加到 β-烷氧基醛; B）将各种烯丙基锡试剂立体控制地添加到 α-烷氧基醛， c）将各种烯丙基锡试剂立体控制地添加到 α-β-二烷氧基醛，形式上进行了立体化学控制 通过α或β-烷氧基， d）醛亚胺以上的化学延伸，以及α和 β-烷氧基醛亚胺。 e）由容易获得的手性化合物不对称合成高烯丙基胺 醛亚胺， f）对新的“单电子”C-C键形成过程的进一步研究， g）杂原子或碳亲核试剂的立体控制加成， 各种γ-取代的不饱和酮、酯和硫醇酯， h）控制上述因素的机理研究 流程和 i）将上述应用于合成具有医学重要性的化合物， 材料，特别是吡咯烷生物碱，卡西霉素，除草霉素 还有麦克霉素和丝裂霉素 应当指出，拟议的《公约》最重要的方面也许是 工作是它几乎普遍适用于生物合成 活性材料。

The proposed research involves the development of many new C-C and C-N bond forming reactions for eventual application to the total synthesis of pharmacologically significant materials, specifically: a) Stereocontrolled additions of various allyltin reagents to Beta-alkoxyaldehydes; b) Stereocontrolled additons of various allyltin reagents to Alpha-alkoxyaldehydes, c) Stereocontrolled additions of various allyltin reagents to Alpha-Beta-dialkoxyaldehydes, with stereochemical control formally exerted by either the Alpha or Beta-alkoxy group, d) The extension of the chemistry above aldimines, and Alpha and Beta-alkoxy aldimines. e) Asymmetric synthesis of homoallyl amines from readily available chiral aldimines, f) Further studies on new "one electron" C-C bond forming processes, g) Stereocontrolled additions of heteroatom or carbon nucleophiles to various Gamma-substituted unsaturated ketones, estaers, and thiol esters, h) Mechanistic investigations of the factors controlling the above processes, and i) Application of the foregoing to the synthesis of medicinally important materials, specifically pyrrolizidne alkaloids, calcimycin, the herbimycins and macbecins, and the mitomycins. It should be noted that perhaps the most significant aspect of the proposed work is its almost universal applicability to the synthesis of biologically active materials.