Construction of chiral reaction environment based on spontaneous resolution of organic compounds

1)以苯磺酰苯胺手性晶体为不对称配体，在二乙基锌和三酸铜的条件下，乙基与查尔酮加成反应。然而，没有观察到任何对映体过量的产物。2)探索了其他磺胺类化合物的自发溶解性。在苯环的o位合成了取代苯磺酰氯和用醚基取代苯胺等，以获得金属配位或较慢的外消旋反应。结果表明，40种磺胺类化合物中有5种具有自发分解性。3)结合聚合物支撑碱平行合成、滤液搅拌蒸发至干燥、固相CD光谱测量等方法，改进了在较短时间内有效搜索到自发分解化合物的方案。根据该程序，通过棉花效应判断，在12种磺酰氯和苯胺的组合中发现了4种磺酰胺。4)在圆偏振光照射下结晶，但磺胺类化合物的对映体比例没有发生手性诱导，表现为自发分解。5)在对芳族磺胺类化合物自发分解的研究过程中，发现所有芳族磺胺类化合物在晶体中均以向斜形式存在，部分芳族磺胺类化合物在分子间形成双氢键。

1)A chiral crystal of benzenesulfonanilide was used as an asymmetric ligand in addition reaction of ethyl group to Chalcone under the condition of diethylzinc and copper triflate. Any enantio excess of products, however, was not observed.2)Other sulfonamides which show spontaneous resolution were explored. Substituted benzenesulfonyl chloride and substituted aniline with ether group etc. at the o-position of the benzene ring for metal coordination or to be slower in racemization were synthesized. In the result, it was found that 5 of 40 sulfoanilides showed spontaneous resolution.3)The protocol in which compounds that show spontaneous resolution are searched effectively in shorter time was modified in combination with parallel synthesis using polymer-supported base, evaporation of filtrate to dryness with stirring, and solid state CD spectrum measurement. According to the procedure, it was found that 4 sulfonamides out of 12 combinations of sulfonyl chlorides and anilines, judging by the Cotton effect.4)Crystallization was carried out under an irradiation of circular polarized light, but chiral induction was not observed in an enantiomer ratio of the sulfonamides which showed spontaneous resolution.5)On the course of the investigation into the spontaneous resolution of aromatic sulfonamides, all the aromatic sulfonamides were found to exist in synclinal form in the crystal, some of which formed in intermolecular double hydrogen bonds.