of the resulting phosphonium salt buildingblocks was demonstrated by the chemoselective post-functionalization of benzylic C(sp3 )-+ PPh3 groups to achieve aminations, thiolations, and arylations. In this way, benzhydrylamines, benzhydrylthioethers, and triarylmethanes, structural motifs that are present in many pharmaceuticals and agrochemicals, are readily accessed. These include the synthesis of
含有 C(sp3 )-+ P 键的有机鏻盐是有机合成中用于构建 CC 双键的最常用试剂之一。然而,它们用作 C 选择性亲电基团的情况很少见。在这里,我们探索了一种有效且通用的无过渡金属方法,用于顺序化学和区域选择性 CH 和 C(sp3 )-+ P 键功能化。在本研究中,CH 烷基化导致二苯甲基三芳基鏻盐的合成是通过简单和市售起始材料的一锅四组分交叉偶联反应实现的。通过对苄基 C(sp3 )-+ PPh3 基团进行化学选择性后官能化以实现胺化、硫醇化和芳基化,证明了所得鏻盐结构单元的实用性。这样,二苯甲基胺、二苯甲基硫醚、和三芳基甲烷是许多药物和农用化学品中存在的结构基序,很容易获得。其中包括仅用两到三个步骤从简单材料合成两种抗癌剂。此外,还开发了使用二苯甲基鏻盐对生物活性药物进行后期功能化的协议。这种新方法应该为学术和药物研究中的应用提供新的转变。
Unlocking the reactivity of diazo compounds in red light with the use of photochemical tools
作者:Katarzyna Orłowska、Klaudia Łuczak、Piotr Krajewski、João V. Santiago、Katarzyna Rybicka-Jasińska、Dorota Gryko
DOI:10.1039/d3cc05174a
日期:——
The red light-irradiation of structurally diversified diazoalkanes gives access to reactive intermediates via direct photolysis and via photosensitization or photoredox approaches.
用红光照射结构多样化的重氮烷烃,可通过直接光解、光敏化或光氧化方法获得反应中间体。
Micro-flow heteroatom alkylation <i>via</i> TfOH-mediated rapid <i>in situ</i> generation of carbocations and subsequent nucleophile addition
作者:Yuma Matsuura、Shinichiro Fuse
DOI:10.1039/d3cc06308a
日期:——
A rapid nucleophilic substitution reaction was developed using carbocations generated from diarylmethanol and trifluoromethanesulfonic acid. Undesired reactions caused by the carbocations were suppressed, presumably due to the rapid and uniform generation of carbocations and the subsequent rapid and uniform distribution of nucleophiles by the micro-flow technology.