CHIRAL APPROACHES TO NATURAL PRODUCT SYNTHESIS

建议的研究涉及许多新的C-C和C-N键的开发 形成最终应用于全合成的反应 具有重要药理意义的材料，特别是： A)各种烯丙基锡试剂的立体控制添加到 β-烷氧基醛； B)各种烯丙基锡试剂的立体控制加成物 α-烷氧基醛， C)各种烯丙基锡试剂的立体控制添加 α-β-二烷氧基醛，已正式实施立体化学控制 通过Alpha或Beta-烷氧基， D)乙二胺以上的化学延伸，以及阿尔法和 β-烷氧基乙二胺。 E)由容易获得的手性化合物不对称合成高烯丙基胺 乙二胺， F)进一步研究新的“单电子”碳-碳键形成工艺， G)杂原子或碳亲核试剂的立体可控加成 各种伽马取代的不饱和酮、酯和硫醇酯， H)对控制上述情况的因素进行机械调查 进程，以及 I)上述化合物在合成具有重要药用价值的化合物中的应用 材料，特别是吡咯里西尼生物碱、钙霉素、除草剂 还有通心粉，还有丝裂霉素。 应该指出的是，也许拟议中的 工作是它几乎普遍适用于生物合成 活性物质。

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.