Synthesis of Optically Pure Enantiomers Using Chiral Ureas

使用手性脲合成光学纯对映体

基本信息

批准号：
03640438
负责人：
YAMADA Kazutoshi
金额：
$ 1.34万
依托单位：
CHIBA University
依托单位国家：
日本
项目类别：
Grant-in-Aid for General Scientific Research (C)
财政年份：
1991
资助国家：
日本
起止时间：
1991 至 1992
项目状态：
已结题

项目摘要

Using Chiral urea derivatives, the following diastereoselective synthesis and a convenient separation of diastereomers by a conventional column chromatography were accomplished.(1) Diastereoselective aldol addition reaction using chiral acylureas; This method was applied to the two step synthesis of (+) Blastmaycinolactol.(2) Chiral carbodiimide as an effective chiral derivatizing agent; N,N'-bis[(s)-l-phenylethyl]- carbodiimide was found to be a very useful chiral derivatizing agent, which made an easy separation of diastereomers of alpha-amino acids and alpha-halo acids by a conventional column chromatography.(3) Highly enantioselective Aldol reaction using imidazolidinone as a new chiral Auxiliary; Aldol addition reaction of almost perfect stereo control (>99% diastereoselectivity) was developed.(4) Chiral hydantoin as a new dienophile for Diels-Alder Reaction; A new synthetic method of chiral exo-methylenehydantoin from chiral carbodiimides and alpha-ketoacids was established and the exo-methylenehydantoin thus obtained was applied for Diels-Alder reaction to prepare chiral bicyclic alpha-amino acid derivatives.(5) Conjugated addition reaction of alkylaluminum compounds to exo-methylenehydantoin; Mono and Double conjugated additions of aluminum reagents to exo-methylenehydantoin were found out and this two modes of addition was effectively controlled.(6) Three component coupling reaction carbodiimide, monomethyl maleate, and alcohol; This coupling afforded N-(aminocarbony)aspartates.(7) Asymmetric type II photocyclization of acrylylureas; It was found that the stereochemistry of the carbon atom where a hydrogen atom to be abstracted in type II photocyclization was retained to give a chiral beta-lactam.

使用手性尿素衍生物，通过传统的色谱柱色谱法实现了以下非对映选择性合成和对非映异构体的方便分离。该方法应用于（+）BlastMaycinolactol的两个步骤合成。（2）手性碳二二酰亚胺作为有效的手性衍生剂； n，n'bis [（s） - l-苯基乙基] - 碳二酰亚胺是一种非常有用的手性衍生物，它使α-氨基酸和α-甲酸的非对映异构体通过常规柱色谱法分离。开发了几乎完美的立体对照（> 99％非对非洲脱位性）的藻类添加反应。（4）手性羟托因作为Diels-Alder反应的新二氧化碳；建立了一种新的手性外甲基甲基乙基乙胆蛋白，从手性碳二酰亚胺和α-酮酸建立了一种新的合成方法，因此将获得的外甲基氢气素用于二甲基乙基甲素蛋白，以使二烷基反应用于alder-Alder反应，以制备手势氨基氨基氨基酸性反应。外甲基乙基甲苯蛋白；发现铝试剂与外甲基甲基胆料素的单一和双重共轭添加，并有效地控制了这两种添加模式。（6）三个成分偶联反应反应反应碳二酰亚胺，单甲基恶核和酒精；这种耦合提供了n-（氨基酸）天冬氨酸。（7）丙烯珠的不对称II型光邻化；发现碳原子的立体化学在其中保留了II型光邻化中要抽象的氢原子以产生手性β-内酰胺。