期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 137, 期 13, 页码 4398-4403出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja512875g
关键词
-
资金
- EPSRC [EP/I038071/1, EP/G036764/1]
- European Research Council [246785]
- Novartis
- Marie Curie Fellowship program (EC) [626828]
- EPSRC [EP/K03927X/1, EP/I038071/1, EP/K035746/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/K035746/1, EP/I038071/1, EP/K03927X/1] Funding Source: researchfish
The iterative homologation of boronic esters using chiral lithiated benzoate esters and chloromethyllithium has been applied to the highly efficient syntheses of two natural products, (+)-kalkitoxin and (+)-hydroxyphthioceranic acid. The chiral lithiated benzoate esters (>99% ee) were generated from the corresponding stannanes, which themselves were prepared by HoppeBeak deprotonation of ethyl 2,4,6-triisopropyl-benzoate with s-BuLi in the presence of (+)- or (-)-sparteine and trapping with Me3SnCl followed by recrystallization. In addition, it was found that purification between several homologations could be avoided, substantially increasing both chemical and manpower efficiency. In the case of (+)-kalkitoxin, six iterative homologations were conducted on commercially available p-MeOC(6)H(4)CH(2)Bpin to build up the core of the molecule before the C-B bond was converted into the desired CN bond, without purification of intermediates. In the case of (+)-hydroxyphthioceranic acid, 16 iterative homologations were conducted on p-MeOC(6)H(4)Bpin with only four intermediate purifications before oxidation of the C-B bond to the desired alcohol. The stereocontrolled and efficient syntheses of these complex molecules highlight the power of iterative chemical synthesis using boronic esters.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据