Rhodium-Catalyzed [4+2+1] Cycloaddition of In Situ Generated Ene/Yne-Ene-Allenes and CO
Rhodium-Catalyzed [4+2+1] Cycloaddition of In Situ Generated Ene/Yne-Ene-Allenes and CO
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铑催化[4 2 1]原位生成烯/炔-烯-丙二烯与CO的环加成
DOI：
10.1002/anie.201805908
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发表时间：
2018
期刊：
影响因子：
--
通讯作者：
Zhi-Xiang Yu
中科院分区：
文献类型：
--
作者：
Tian Zi-You;Qi Cui;Cheng-Hang Liu;Zhi-Xiang Yu
本文报道了第一个铑催化的原位生成的烯/炔-烯-丙二烯和CO的[4+2+1]环加成反应，以合成具有挑战性的与五元环稠合的七元碳环。该反应的设计基于烯/炔-烯-炔丙酯的1,3-酰氧基迁移为烯/炔-烯-丙二烯，然后氧化环化、CO插入和还原消除，形成最终的[4+2+1]环加合物。不利于可能的竞争性[4+1]、[4+2]和[2+2+1]环加成，使得本反应成为获得官能化5/7环的有效方法。
Reported herein is the first rhodium‐catalyzed [4+2+1] cycloaddition of in situ generated ene/yne‐ene‐allenes and CO to synthesize challenging seven‐membered carbocycles fused with five‐membered rings. This reaction is designed based on the 1,3‐acyloxy migration of ene/yne‐ene‐propargyl esters to ene/yne‐ene‐allenes, followed by oxidative cyclization, CO insertion, and reductive elimination to form the final [4+2+1] cycloadducts. The possible competing [4+1], [4+2], and [2+2+1] cycloadditions were disfavored, making the present reaction an efficient way to access functionalized 5/7 rings.