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基于Brook重排反应的1,2-二胺及α-羟基-β-氨基酸衍生物的合成方法研究
林朝阳
Subtype博士
Thesis Advisor卢崇道
2015-06-01
Degree Grantor中国科学院大学
Place of Conferral北京
Degree Discipline有机化学
KeywordBrook重排 二苯基次膦酰亚胺 Anti-1 硅基酮亚胺 2-二胺 酰硅
Abstract

多组分反应可以通过简单易得的原料直接合成结构多样的化合物,一直以来备受人们的关注,Brook重排介导的多组分反应在有机合成化学中得到了广泛的应用。然而有关硅基由碳原子到氮原子的迁移(aza-Brook rearrangement)的报道较少,有关aza-Brook重排反应在有机合成中的应用更是鲜有报道。本论文首先研究了通过aza-Brook重排引发的α-硅基胺与二苯基次膦酰亚胺的反应合成不对称anti-1,2-二胺的方法。六甲基二硅基氨基钾(KHMDS)可以高效地诱发α-硅基胺发生[1,2]-aza-Brook而产生α-胺基负离子,该碳负离子与二苯基次膦酰亚胺发生亲核加成反应,以较好的收率和立体选择性得到不对称的anti-1,2-二胺。其次我们研究了通过二甲基苯基硅基锂试剂与亚胺酸酯的加成反应来制备酰硅和硅基酮亚胺的方法。二甲基苯基硅基锂试剂与亚胺酸酯加成后在不同的条件下淬灭反应可得到不同的产物,使用1 N的稀盐酸淬灭反应可以得到硅基酮亚胺,使用6 N的盐酸淬灭反应可以得到酰硅。最后我们对Brook重排介导的甲酰胺、酰硅、亚胺三组分制备α-季碳-α-羟基-β-氨基酰胺进行了初步的研究。甲酰胺在LDA的作用下可以得到相应羰基碳负离子,该负离子与酰硅加成后经硅基重排得到的碳负离子中间体与二苯基次膦酰亚胺反应可以以较好的产率(>90%)和立体选择性(dr>20:1)得到α-季碳-α-羟基-β-氨基酰胺。

Other Abstract
Multicomponent reaction have aroused attention as tools for the rapid generation of complex and functionally diverse sets of compounds. The Brook rearrangement was found to play an important role in the discovery of novel reactions over the past decade. However, the studies involving silyl migration from a carbon to a nitrogen atom (aza-Brook rearrangement) and their applications in synthesis are relatively rare. In the first part, we have described the anti-selective synthesis of symmetrical and unsymmetrical 1,2-diaryl-1,2-diamines via aza-Brook rearrangement-initiated nucleophilic addition of α-silylamines to imines. KHMDS was used as base to induce the [1,2]-aza-Brook rearrangement of aryl α-silylamine to afford α-amino carbanion, which was subsequently intercepted by the imine to give the anti-diamine after desilylation in moderate to high yields with high anti/syn diastereoselectivity. Furthermore, we have investigated the synthesis of acylsilane and acylsilane-derived imine from sulfonylimidates. The additions of silyllithium (PhMe2SiLi) to methyl N-Ts-phenylimidates give acylsilanes after workup under strong acidic quenching conditions (6 N aqueous HCl), while acylsilane-derived imines were obtained by using 1.0 N aqueous HCl. Finally, we have developed three-component reactions of formamides, acylsilanes, and imines to give α-quaternary α-hydroxy-β-amino amides. The N,N-disubstituted formamides were deprotonated in the presence of LDA to generate carbamoyl anions that reacted with acylsilanes to form new nucleophilic intermediates after silyl migration. Subsequent electrophilic trapping of the intermediates by imines to give α-quaternary α-hydroxy-β-amino amide in high yields with high diastereoselectivity.
Document Type学位论文
Identifierhttp://ir.xjipc.cas.cn/handle/365002/4269
Collection资源化学研究室
Affiliation中国科学院新疆理化技术研究所
Recommended Citation
GB/T 7714
林朝阳. 基于Brook重排反应的1,2-二胺及α-羟基-β-氨基酸衍生物的合成方法研究[D]. 北京. 中国科学院大学,2015.
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