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石蒜科生物碱家族中羟基菲啶酮亚类某些成员的合成。

Synthesis of some members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family.

作者信息

Padwa Albert, Zhang Hongjun

机构信息

Department of Chemistry, Emory University, Atlanta, Georgia 30322, USA.

出版信息

J Org Chem. 2007 Mar 30;72(7):2570-82. doi: 10.1021/jo0626111. Epub 2007 Mar 6.

DOI:10.1021/jo0626111
PMID:17338575
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC2475589/
Abstract

The total synthesis of several members of the hydroxylated phenanthridone subclass of the Amaryllidaceae alkaloid family has been carried out. (+/-)-Lycoricidine and (+/-)-7-deoxypancratistatin were assembled through a one-pot Stille/intramolecular Diels-Alder cycloaddition cascade to construct the core skeleton. The initially formed [4+2]-cycloadduct undergoes nitrogen-assisted ring opening followed by a deprotonation/reprotonation of the resulting zwitterion to give a rearranged hexahydroindolinone on further heating at 160 degrees C. The stereochemical outcome of the IMDAF cycloaddition has the side arm of the tethered vinyl group oriented exo with respect to the oxygen bridge. The resulting cycloadduct was used for the stereocontrolled installation of the remaining functionality present in the C-ring of the target molecules. Key features of the synthetic strategy include (1) a lithium hydroxide induced tandem hydrolysis/decarboxylation/elimination sequence to introduce the required pi-bond in the C-ring of (+/-)-lycoricidine, and (2) conversion of the initially formed Diels-Alder adduct into an aldehyde intermediate which then undergoes a stereospecific decarbonylation reaction mediated by Wilkinson's catalyst to set the trans-B-C ring junction of (+/-)-7-deoxypancratistatin.

摘要

已经完成了石蒜科生物碱家族中羟基菲啶酮亚类几个成员的全合成。（±）-石蒜碱和（±）-7-脱氧水仙环素通过一锅法施蒂勒反应/分子内狄尔斯-阿尔德环加成串联反应构建核心骨架。最初形成的[4+2]环加成物在氮的作用下开环，随后所得两性离子进行去质子化/再质子化，在160℃进一步加热时得到重排的六氢吲哚酮。分子内狄尔斯-阿尔德环加成反应的立体化学结果是，连接的乙烯基侧链相对于氧桥向外取向。所得环加成物用于立体控制引入目标分子C环中存在的其余官能团。合成策略的关键特征包括：（1）氢氧化锂诱导的串联水解/脱羧/消除序列，以在（±）-石蒜碱的C环中引入所需的π键；（2）将最初形成的狄尔斯-阿尔德加合物转化为醛中间体，然后该醛中间体在威尔金森催化剂介导下进行立体特异性脱羰反应，以确定（±）-7-脱氧水仙环素的反式B-C环连接。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/e363/2475589/d63ce84f3698/nihms57699f14.jpg
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