In Situ-Generated Iodonium Ylides as Safe Carbene Precursors for the Chemoselective Intramolecular Buchner Reaction
In Situ-Generated Iodonium Ylides as Safe Carbene Precursors for the Chemoselective Intramolecular Buchner Reaction
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原位生成的碘叶立德作为化学选择性分子内布赫纳反应的安全卡宾前体
DOI：
10.1021/jo501628h
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发表时间：
2014
影响因子：
3.6
通讯作者：
Xu Jiaxi
中科院分区：
文献类型：
--
作者：
Mo Shanyan;Li Xinhao;Xu Jiaxi
发展了一种以碘叶立德为安全卡宾前体的化学选择性分子内Buchner反应。在碱存在下，N-苄基-2-氰基乙酰胺和PhI（OAc）2原位生成碘鎓叶立德，在Cu（OAc）2·H2O催化下发生分子内Buchner反应，得到稠合环庚-1，3，5-三烯衍生物，产率高达85%。具有两个不同苄基的N，N-二苄基-2-氰基乙酰胺选择性地在其富电子苄基上发生分子内Buchner反应。该反应对空气和水分不敏感，并使用相应重氮起始物料的安全替代形式。已验证了涉及卡宾途径的整体转化。
A chemoselective intramolecular Buchner reaction employing iodonium ylides as safe carbene precursors has been developed. Iodonium ylides are generated in situ fromN-benzyl-2-cyanoacetamides and PhI(OAc)2in the presence of base and undergo intramolecular Buchner reaction under catalysis from Cu(OAc)2·H2O, affording fused cyclohepta-1,3,5-triene derivatives in up to 85% yield. TheN,N-dibenzyl-2-cyanoacetamides with two different benzyl groups undergo intramolecular Buchner reaction on their electron-rich benzyl groups selectively. The reaction is not sensitive to air and moisture and uses a safe alternative version of the corresponding diazo starting materials. The overall transformation involving the carbene pathway has been verified.