Development of a Highly Stereoselective Remote Asymmetric Induction Method by Means of the Binaphthalene-Template Conformation Control

我们利用1,1 ‘-联萘基化合物的2,2’位作为手性场，开发了非对映选择性不对称反应。本文的另一个研究目标是合成新的二萘和硫杯芳烃，并探索后者的功能。结果总结如下：在溴化镁的存在下，用DIBAL-H处理1,1′-二苯基-2-醇的-酮酯，在2′位置上含有适当的低聚醚系醚，在LAH还原得到非对映体羟基酯后，得到具有高对映体过量的1,4 -二醇。另一方面，相关的γ -酮酯通过格氏反应得到具有手性季碳中心的γ -内酯，其ee含量高达99%。2. 发现远距离不对称诱导格氏反应适用于δ -和ε -酮酯，有利于海洋抗生素马林内酯的合成。3. 以二酚为手性助剂，实现了ζ -到θ -酮酯的格氏反应。因此，在溴化镁的存在下，双酚单ω -酮酯的格氏反应进行了80%以上。用1-萘格氏试剂在1-烷氧炔上以2位的酯、磺酰基或硝基为活化基团，通过亲核芳代取代，以atro异构或外消旋形式有效地制备了几种双萘基化合物。5. 以对叔丁基苯酚和粉末硫为原料，制备了一种新型杯芳烃对叔丁基thiacalix[4]芳烃，有望成为BINOL骨架的潜在替代品。这些衍生物被发现作为宿主分子结合特定的金属离子和有毒的卤化有机化合物，并作为气相色谱固定相的手性识别元素。

We have developed diastereoselective asymmetric reactions using the 2,2'-positions of 1, l'-binaphthyl compounds as a chiral field. Synthesis of novel binaphthyls and thiacalixarenes and exploration of the functions of the latter compounds are the other targets of this research. The summary of the results is itemized as follows : 1. Treatment of gamma-keto esters of l , 1'-binaphthyl-2-ol bearing an appropriate oligoether tether at the 2'-position with DIBAL-H in the presence of magnesium bromide gave, after LAH reduction of the resulting diastereomeric hydroxy esters, I , 4-diols with high enantiomeric excesses. On the other hand, Grignard reaction of the relevant gamma-keto esters gave gamma-lactones having a chiral quaternary carbon center with up to 99% ee. 2. The remote asymmetric inductive Grignard reaction was found to be applicable to delta- and epsilon-keto esters and was advantageously utilized for the synthesis of a marine antibiotic, malyngolide. 3. The corresponding Grignard reaction of zeta- to theta-keto esters was realized by using BINOL as the chiral auxiliary. Thus, the Grignard reaction of the mono omega-keto esters of BINOL in the presence of magnesium bromide proceeded with more than 80% de. 4. Several binaphthyl compounds were effectively prepared in an atropisomeric or racemic form via the nucleophilic aromatic substitution on 1-alkoxynaphthalenes bearing an ester, sulfonyl, or nitro group at the 2-position as the activating group by 1-naphthyl Grignard reagents. 5. A novel calixarene, p-tert-butylthiacalix[4]arene, which is expected to be a potential substitute for BINOL framework, was effectively prepared from p-tert-butylphenol and powdered sulfur. The derivatives were found to function as a host molecule to bind specific metal ions and toxic halogenated organic compounds and as a chirality-recognizing element for a stationary phase for gas chromatography.