[3,3]-Sigmatropic rearrangement/5-exo-dig cyclization reactions of benzyl alkynyl ethers: synthesis of substituted 2-indanones and indenes.
[3,3]-Sigmatropic rearrangement/5-exo-dig cyclization reactions of benzyl alkynyl ethers: synthesis of substituted 2-indanones and indenes.
复制标题
苄基炔基醚的[3,3]-Sigmatropic重排/5-exo-dig环化反应：取代的2-茚满酮和茚的合成。
DOI：
10.1021/jo200271s
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发表时间：
2011
期刊：
影响因子：
--
通讯作者：
Minehan,ThomasG
中科院分区：
文献类型：
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作者：
Tudjarian,ArmenA;Minehan,ThomasG
取代苄基炔基醚是由相应的α-烷氧基酮经过三烯酸酯形成和kotbu2诱导E2消除两步反应制得的，在60℃下经过[3,3]-异位重排/分子内5-外二环化，生成取代的2-吲哚酮，总产率较高。1,3-顺式-二取代-2-吲哚酮在苯基取代基r1体积较大时优先形成。用Horner - Wadsworth - Emmons反应可以高产地制备取代茚酮。
Substituted benzyl alkynyl ethers, prepared from the corresponding α-alkoxy ketones in a two-step sequence involving enol triflate formation and KOtBu-induced E2 elimination, undergo [3,3]-sigmatropic rearrangement/intramolecular 5-exo-digcyclization at 60 °C to form substituted 2-indanones in good overall yields. 1,3-cis-Disubstituted-2-indanones are formed preferentially when the benzylic substituent R1is bulky. Substituted indenes may be prepared from 2-indanones in high yields by Horner−Wadsworth−Emmons reaction.