铑催化的 3-酰氧基-1,4-烯炔和炔烃的分子内和分子间[5+2]环加成反应以及伴随的 1,2-酰氧基迁移。
Rhodium-catalyzed intra- and intermolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkyne with concomitant 1,2-acyloxy migration.
机构信息
School of Pharmacy, University of Wisconsin, Madison, Wisconsin 53705, United States.
出版信息
J Am Chem Soc. 2012 Mar 21;134(11):5211-21. doi: 10.1021/ja2109097. Epub 2012 Mar 12.
Abstract
A new type of rhodium-catalyzed [5 + 2] cycloaddition was developed for the synthesis of seven-membered rings with diverse functionalities. The ring formation was accompanied by a 1,2-acyloxy migration event. The five- and two-carbon components of the cycloaddition are 3-acyloxy-1,4-enynes (ACEs) and alkynes, respectively. Cationic rhodium(I) catalysts worked most efficiently for the intramolecular cycloaddition, while only neutral rhodium(I) complexes could facilitate the intermolecular reaction. In both cases, electron-poor phosphite or phosphine ligands often improved the efficiency of the cycloadditions. The scope of ACEs and alkynes was investigated in both the intra- and intermolecular reactions. The resulting seven-membered-ring products have three double bonds that could be selectively functionalized.
摘要
开发了一种新型的铑催化[5+2]环加成反应，用于合成具有各种官能团的七元环。环形成伴随着 1,2-酰氧基迁移事件。环加成的五碳和两碳组分分别是 3-酰氧基-1,4-烯炔（ACE）和炔烃。阳离子铑（I）催化剂对分子内环加成反应最有效，而只有中性铑（I）配合物才能促进分子间反应。在这两种情况下，缺电子的亚磷酸酯或膦配体通常可以提高环加成反应的效率。在分子内和分子间反应中都研究了 ACE 和炔烃的范围。所得的七元环产物具有三个双键，可以选择性官能化。
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