Development of Novel Carbanion Rearrangements as a Stereoselective Approach toward Heteroatom-containing Natural Products

在杂官能化体系中发展了以下新型碳离子反应：1 .氧体系a)环缩醛的扩环[2,3]-Wittig重排：中型环乙烯基醚的立体选择方法。b)环缩[1,2]-Wittig重排：中等大小环醚的立体选择方法。c)环缩醛体系阴离子环缩反应：多功能化氧烷的立体选择方法。d)[1,4]-含乙基乙烯基甲醇衍生迁移末端的wittig重排：串联重排-醛醇反应。ii . aza系统a)环状放大aza-[1,2]和[2,3]-环状半聚物重排。b) Sn-Li转金属诱导的不对称za- wirtig重排。c)邻苯二胺衍生炔基半胺的序贯碳离子反应：四组分偶联制备多取代吡咯的高效方法。d)环半缩醛体系的Stevens重排：手性α-氨基酮的非对映选择方法。

The following novel carbanion reactions of hetero-functionalized system have been developed.I.Oxy systema)Ring-enlarging [2,3]-Wittig rearrangement of cyclic acetals : Stereoselective approach to medium-sized cyclic vinyl ethers.b)Ring-contracting [1,2]-Wittig rearrangement of cyclic acetals : Stereoselective approach to medium-sized cyclic ethers.c)Anionic ring-contraction reaction of cyclic acetal system : Stereoselective approach to multi-functionalized oxetanes.d)[1,4]-Wittig rearrangement containing ethynylvinylmethanol-derived migration terminus : Tandem rearrangement-aldol reaction.II.Aza systema)Ring-enlarging aza-[1,2] and [2,3]-rearrangement of cyclic hemiaminals.b)Asymmetric aza-Wirtig rearrangement induced by Sn-Li transmetalation.c)The sequential carbanion reactions of phthalimide-derived alkynyl hemiaminal: Efficient approach to polysubstituted pyrrole via four components coupling.d)Stevens rearrangement of a cyclic hemiacetal system: Diastereoselective approach to chiral α-amino ketone.