Exploiting Configurational Lability in Aza-Sulfur Compounds for the Organocatalytic Enantioselective Synthesis of Sulfonimidamides.
Exploiting Configurational Lability in Aza-Sulfur Compounds for the Organocatalytic Enantioselective Synthesis of Sulfonimidamides.
复制标题
DOI：
10.1002/anie.202109160
复制
发表时间：
2021-12-01
影响因子：
16.6
通讯作者：
Willis, Michael C.
中科院分区：
文献类型：
--
作者：
Tilby, Michael J.;Dewez, Damien F.;Hall, Adrian;Martinez Lamenca, Carolina;Willis, Michael C.
确定硫磺立体生成氮杂硫衍生物的绝对构型的方法很少，通常依赖于繁琐的程序和有限的对映体富集库。我们首次利用磺胺类化合物的一个特征解决了这个问题，在这个特征中，互变异构体结构也可能是对映异构体。这种磺酰亚胺很容易产生前手性离子，我们已经在对映选择性烷基化过程中利用了这一点。选择性是使用易于制备的双季铵盐化相转移催化剂实现的。整个过程建立了构型不稳定的氮杂硫物种用于不对称催化的能力。某些磺胺类化合物具有不寻常的立体化学特征，其中互变异构体也是对映异构体，已被用来开发一种催化对映体选择性合成烷基磺酰亚胺类化合物。这些反应通过前手性阴离子中间体进行，产生对映体富集物。双烷基化的金鸡纳生物碱衍生催化剂被用作相转移催化剂。
Methods for establishing the absolute configuration of sulfur‐stereogenic aza‐sulfur derivatives are scarce, often relying on cumbersome protocols and a limited pool of enantioenriched starting materials. We have addressed this by exploiting, for the first time, a feature of sulfonimidamides in which it is possible for tautomeric structures to also be enantiomeric. Such sulfonimidamides can readily generate prochiral ions, which we have exploited in an enantioselective alkylation process. Selectivity is achieved using a readily prepared bis‐quaternized phase‐transfer catalyst. The overall process establishes the capability of configurationally labile aza‐sulfur species to be used in asymmetric catalysis. The unusual stereochemical feature of certain sulfonimidamides, in which tautomeric forms are also enantiomeric, has been exploited to develop a catalytic enantioselective synthesis of alkylated sulfonimidamides. The reactions proceed through a prochiral anionic intermediate to deliver enantiomerically enriched products. A double‐alkylated, cinchona alkaloid‐derived catalyst is used as a phase‐transfer catalyst.
登录
查看更多内容
影响因子：
4.3
作者：
Bandini, Marco;Bottoni, Andrea;Stenta, Marco
通讯作者：
Stenta, Marco
影响因子：
3.6
作者：
Bayer, A;Endeshaw, MM;Gautun, OR
通讯作者：
Gautun, OR
影响因子：
3.4
作者：
Borhade, Sanjay R.;Svensson, Richard;Sandstroem, Anja
通讯作者：
Sandstroem, Anja
影响因子：
16.6
作者：
Bremerich, Maximilian;Conrads, Christian M.;Bolm, Carsten
通讯作者：
Bolm, Carsten
影响因子：
5.2
作者：
Borhade, Sanjay R.;Sandstrom, Anja;Arvidsson, Per I.
通讯作者：
Arvidsson, Per I.