Copper-Catalyzed Reductive Ireland–Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates,The Journal of Organic Chemistry

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Copper-Catalyzed Reductive Ireland–Claisen Rearrangements of Propargylic Acrylates and Allylic Allenoates
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2021-12-17 , DOI: 10.1021/acs.joc.1c02455
Siyuan Guo ₁ , Kong Ching Wong ₁ , Stephan Scheeff ₁ , Zhuo He ₁ , Wesley Ting Kwok Chan ₂ , Kam-Hung Low ₁ , Pauline Chiu ₁

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The copper-catalyzed reductive Ireland–Claisen rearrangement of propargylic acrylates led to 3,4-allenoic acids. The use of silanes or pinacolborane as stoichiometric reducing agents and triethylphosphite as a ligand facilitated the divergent and complementary selectivity for the synthesis of diastereomeric anti- and syn-rearranged products, respectively. Copper-catalyzed reductive Ireland–Claisen rearrangement of allylic 2,3-allenoates proceeded effectively only when pinacolborane was used as a reductant to generate various 1,5-dienes in excellent yields and with good diastereoselectivities in some cases. Mechanistic studies showed that the silyl and boron enolates, rather than the copper enolate, underwent a stereospecific rearrangement via a chairlike transition state to afford the corresponding Claisen rearrangement products.

中文翻译：

丙炔丙烯酸酯和烯丙基烯丙酸酯的铜催化还原爱尔兰-克莱森重排

炔丙基丙烯酸酯的铜催化还原爱尔兰-克莱森重排产生 3,4-丙二烯酸。硅烷或频哪醇硼烷作为化学计量还原剂和亚磷酸三乙酯作为配体的使用促进了合成非对映体反-和顺的发散和互补选择性-重新排列的产品，分别。仅当频哪醇硼烷用作还原剂以优异的收率和在某些情况下具有良好的非对映选择性时，铜催化的还原爱尔兰-克莱森重排才能有效地进行烯丙基 2,3-烯丙酸酯。机理研究表明，甲硅烷基和硼烯醇化物，而不是铜烯醇化物，通过椅状过渡态进行立体定向重排，得到相应的克莱森重排产物。

更新日期：2022-01-07

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