De Novo Synthesis of the DEF-Ring Stereotriad Core of the Veratrum Alkaloids
De Novo Synthesis of the DEF-Ring Stereotriad Core of the Veratrum Alkaloids
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DOI：
10.1021/acs.joc.0c00685
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发表时间：
2020-05-15
影响因子：
3.6
通讯作者：
Johnson, Jeffrey S.
中科院分区：
文献类型：
--
作者：
Horwitz, Matthew A.;Robins, Jacob G.;Johnson, Jeffrey S.
报道了藜芦生物碱jervine（1），cyclopamine（2）和rectamine（3）东部立体三单元核的合成。从已知的β-甲基酪氨酸衍生物（8）开始，该路线利用非对映选择性底物控制的1，2-还原来建立嵌入靶标内的邻位氨基醇基序的立体化学。氧化脱芳构化被证明是一种可行的方法，用于合成在jervine和cyclopamine中发现的螺环DE环连接。
The synthesis of the stereotriad core in the eastern portion of the Veratrum alkaloids jervine (1), cyclopamine (2), and veratramine (3) is reported. Starting from a known beta-methyltyrosine derivative (8), the route utilizes a diastereoselective substrate-controlled 1,2-reduction to establish the stereochemistry of the vicinal amino alcohol motif embedded within the targets. Oxidative dearomatization is demonstrated to be a viable approach for the synthesis of the spirocyclic DE ring junction found in jervine and cyclopamine.