Gold(I)‐Catalyzed Alkynylation of N,O‐Acetals: An Access to Alkynylated Saturated N‐heterocycles
Gold(I)‐Catalyzed Alkynylation of N,O‐Acetals: An Access to Alkynylated Saturated N‐heterocycles
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金(I)催化N,O-缩醛的炔基化：获得炔基化饱和N-杂环
DOI：
10.1002/adsc.202300058
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发表时间：
2023
期刊：
影响因子：
--
通讯作者：
V. Michelet
中科院分区：
文献类型：
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作者：
R. Melot;S. Olivero;V. Michelet
已经开发了通过Shono氧化和金（I）催化的炔基化反应的顺序组合来制备炔基化饱和N-杂环的合成路线。电化学Shono氧化允许通过环胺的直接C-H键官能化有效地获得各种N，O-缩醛。反应条件适用于官能化的吡咯烷、四氢异喹啉和吡咯烷-环丙基稠合双环骨架。金催化的过程允许引入带有供电子和适度吸电子的芳基乙炔配偶体。金工艺的效率是显著的，并且可以放大到5 mmol的N，O-缩醛。 基于炔的反应性进行后官能化反应，显示了我们方法的广泛兴趣。获得了关于不对称版本的有希望的初步结果（e.r.高达84.5：15.5）。
A synthetic route for the preparation of alkynylated saturated N‐heterocycles via a sequential combination of a Shono oxidation and a gold(I)‐catalyzed alkynylation reaction has been developed. The electrochemical Shono oxidation allowed an efficient access to a variety ofN,O‐acetals via a direct C−H bond functionalization of cyclic amines. The reaction conditions were amenable with functionalized pyrrolidine, tetrahydroisoquinoline and pyrrolidine‐cyclopropyl fused bicyclic skeletons. The gold‐catalyzed process allowed the introduction of aryl acetylene partners bearing electron‐donating and moderate electron‐withdrawing. The efficiency of the gold process is remarkable and could be scaled up to 5 mmol ofN,O‐acetal. Post‐functionalization reactions were performed based on the reactivity of the alkyne, showing the broad interest of our methodology. Promising preliminary results on an asymmetric version were obtained (e.r. up to 84.5:15.5).