农药的有机合成讲义.pptVIP

It should also be noted here, that under the conditions of “kinetic control” no non- ionized carbonyl compound is present. Therefore nucleophilic addition of the enolate to the carbonyl group is prevented and aldol (羟醛缩合)type side reactions are suppressed.（动力学控制抑制羟醛缩合 ） A carbonyl function may be converted to an imino group by condensation with a primary amine. The resulting N- alkylimine (“Schiff base”) can be metallated with LDA in ether solvents at 0 °C. （可于伯胺形成席夫碱，和LDA在乙醚存在下，在0 °C可发生金属化反应） At -70 °C such lithiated Schiff bases are stable against self-addition. These carbanions are useful in selective aldol additions . 在-70 °C下，碳负离子稳定，自身不缩合. Metallated dimethylhydrazones have also been used extensively. They allow stereo- and regioselective anion formation since the di- methylamino group orients away from large substituents and tends to locate the metal ion on the less substituted carbon atom. 金属和的二甲基腙也被广泛使用，大的二甲基胺基-------负离子趋向—少取代的碳原子上。 低温，大体积碱---反式烯醇盐 R2BOSO2CF3-----------反式烯醇盐 环状亚胺酯 –杂环是潜在的甲酰基或羧酸基 可形成手性碳负离子 烯胺—有用的电中d2试剂，大体积的杂环取代基有利于区域选择性和立体选择性反应。 N-的碱性（四氢吡咯＞哌啶＞ 吗啉）越大—形成烯胺分子的离蜮越大。 1.1.3 d3-Synthons 卡宾化合物对C=C双键加成所的取代环氧丙烷是d3-Synthons。 SO CH Mes = 2 3 Mes ==-SO2CH3 1.1.4 dn-Synthons n＞3的合成子比较独特，参与反应的官能团和不参与反应的官能团不发生作用 四甲基乙二胺 TMEDA 1.2 Electron Acceptors (Electrophiles, a-Synthons) 1.3 Umpolung 交换杂原子 引入杂原子 碳碎片的加成 一些典型的电子接受体和供电子体合成子 1.4 Introduction of Non-functional Alkyl and Reactive Allyl Groups The introduction of additional alkyl groups mostly involves the formation of a bond between a carbanion and a carbon attached to a suitable leaving group. SN2-reactions prevail, although radical mechanisms are also possible, especially if organometallic compounds are involved. Since many carbanions and radicals are easily oxidized by oxygen, working under inert gas is advised The following aspects are important for alleviation reactions in the synthesis of complex molecules and will be exemplified: ? regio- and stereoselective alleviation of С—H, С—Hal, and