焦脱镁叶绿酸与重氮烷的重排反应及其叶绿素衍生物的合成

Rearrangement Reactions of Pyropheophorbide with Diazoalkane and Synthesis of Chlorophyll Derivatives

以焦脱镁叶绿酸-a甲酯及其N^(21)-N^(23)轴向酰化和烯化的衍生物为起始原料,环上碳碳双键或碳氧双键与重氮烷发生1,3-偶极环加成、Michael加成和Tiffeneau-Demjanov重排反应,在周环上的不同位置上形成新的杂环和羰基结构,完成了一系列未见报道的叶绿素类二氢卟吩衍生物的合成.同时,基于相应的反应机理,讨论了重排过程的区域和立体选择性.

Pyropheophorbide-a methyl ester and its derivatives acidylated and alkenylated along the N21-N23 axis were used as starting materials.The 1,3-dipolar cyclocaddition,Michael addition and Tiffeneau-Demjanov rearrangement reaction can smoothly occur with diazoalkane through the carbon-oxygen or carbon-carbon double bonds attached to the periphery to gen- erate new heterocyclic and carbonylic structures in different positions.The synthesis of a series of unreportedchlorins related to chlorophyll was accomplished and their chemical structures were characterized by elemental analysis,UV-Vis,IR,MS and 1H NMR spectra.Meanwhile,the region-and stereo-selectivities of rearrangement processes were discussed based on relevant reaction mechanism.