Conversion of allylic alcohols into allylic nitromethyl compounds via a palladium-catalyzed solvolysis: An enantioselective synthesis of an advanced carbocyclic nucleoside precursor
Conversion of allylic alcohols into allylic nitromethyl compounds via a palladium-catalyzed solvolysis: An enantioselective synthesis of an advanced carbocyclic nucleoside precursor
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DOI：
10.1021/jo951510s
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发表时间：
1996-05-31
影响因子：
3.6
通讯作者：
Aydin, N
中科院分区：
文献类型：
--
作者：
Deardorff, DR;Savin, KA;Aydin, N
介绍了由烯丙醇制均烯丙基硝基化合物的两步反应顺序。这些醇与氯甲酸乙酯的乙氧基羰基化反应可高产得相应的烯丙基碳酸乙酯。将这些底物暴露于催化钯(0)的CH3NO2中会引发一系列反应，电离-脱羧-硝基甲基化，最终形成硝基烯烃。硝基甲基烯丙基化反应的区域和立体化学结果可以用瞬态烯丙基钯配合物的行为来解释。这种方法是合成一种重要的碳环核苷中间体的核心。
A two-step reaction sequence to homoallylic nitro compounds from allylic alcohols is presented. Ethoxy carbonylation of the alcohols with ethyl chloroformate provides the corresponding allylic ethyl carbonates in high yields. Exposure of these substrates to catalytic palladium(0) in CH3NO2 initiates a reaction sequence, ionization - decarboxylation - nitromethylation, that culminates with the formation of nitroalkenes. The regio- and stereochemical outcomes of the nitromethyl allylation reaction can be explained by the behavior of the transient pi-allylpalladium complexes. This methodology serves as a centerpiece for the synthesis of an important carbocyclic nucleoside intermediate.