用于钯催化不对称烯丙基烷基化反应的新型亲核试剂。阿格拉他汀A的全合成。
New class of nucleophiles for palladium-catalyzed asymmetric allylic alkylation. Total synthesis of agelastatin A.
作者信息
Trost Barry M, Dong Guangbin
机构信息
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
出版信息
J Am Chem Soc. 2006 May 10;128(18):6054-5. doi: 10.1021/ja061105q.
Abstract
New classes of nucleophiles, pyrroles, and N-methoxyamides were developed for Pd-catalyzed AAA reactions. By varying the functional groups at the 2-position of pyrroles, either regioisomer of the piperazinone is available. Using one regioisomer, the total synthesis of (+)-agelastatin A in 10 total steps is accomplished. For this synthesis, a new copper-catalyzed aziridination and an indium-catalyzed oxidative ring opening of a N-tosylaziridine were developed. The feasibility of accessing (-)-agelastatin A from the same enantiomer of the chiral catalyst from the other regioisomeric piperazinone is indicated.
摘要
为钯催化的AAA反应开发了新型亲核试剂、吡咯和N-甲氧基酰胺。通过改变吡咯2-位的官能团，可以得到哌嗪酮的任一区域异构体。使用其中一种区域异构体，以总共10步完成了(+)-阿格拉他汀A的全合成。对于该合成，开发了一种新的铜催化氮杂环丙烷化反应以及铟催化的N-甲苯磺酰基氮杂环丙烷的氧化开环反应。结果表明，从另一种区域异构哌嗪酮的手性催化剂的相同对映体获得(-)-阿格拉他汀A是可行的。
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