ENANTIOSPECIFIC AND STEREOSPECIFIC RHODIUM(I)-CATALYZED CARBONYLATION AND RING EXPANSION OF AZIRIDINES - ASYMMETRIC-SYNTHESIS OF BETA-LACTAMS AND THE KINETIC RESOLUTION OF AZIRIDINES
ENANTIOSPECIFIC AND STEREOSPECIFIC RHODIUM(I)-CATALYZED CARBONYLATION AND RING EXPANSION OF AZIRIDINES - ASYMMETRIC-SYNTHESIS OF BETA-LACTAMS AND THE KINETIC RESOLUTION OF AZIRIDINES
复制标题
DOI：
10.1021/ja00185a023
复制
发表时间：
1989-02-01
影响因子：
15
通讯作者：
ALPER, H
中科院分区：
文献类型：
--
作者：
CALET, S;URSO, F;ALPER, H
铑（I）配合物催化氮丙啶到β-内酰胺的区域特异性扩环-羰基化反应。该过程是立体特异性和对映体特异性的，发生时保留构型[例如，（S）-1-叔丁基-2-苯基氮杂环丙烷转化为（S）-1-叔丁基-3-苯基氮杂环丁烷-2-酮]。以氯代（1，5-环辛）铑（I）二聚体为催化剂，d-或l-薄荷醇为手性试剂，由外消旋氮杂环丙烷合成高光学纯度β-内酰胺。回收的氮丙啶也获得了很好的光学产率。
Rhodium (I) complexes catalyze the regiospecific ring expansion-carbonylation reaction of aziridines to/3-lactams. This process is both stereospecific and enantiospecific, occurring with retention of configuration [eg,(S)-l-tm-butyl-2-phenylaziridine is converted to (5)-1-ZerZ-butyl-3-phenylazetidin-2-one]. The synthesis of/3-lactams in high opticalpurity, from racemic aziridines, can be realized by using the dimer of chloro (1, 5-cyclooctadiene) rhodium (I) as the catalyst and d-or/-menthol as an added chiral agent. The recovered aziridine is also obtained infine optical yield.