Rhodium-catalyzed intra- and intermolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkyne with concomitant 1,2-acyloxy migration.
Rhodium-catalyzed intra- and intermolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkyne with concomitant 1,2-acyloxy migration.
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DOI：
10.1021/ja2109097
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发表时间：
2012-03-21
影响因子：
15
通讯作者：
Tang, Weiping
中科院分区：
文献类型：
--
作者：
Shu, Xing-Zhong;Li, Xiaoxun;Shu, Dongxu;Huang, Suyu;Schienebeck, Casi M.;Zhou, Xin;Robichaux, Patrick J.;Tang, Weiping
发展了一种新型的铑催化的[5+2]环加成反应，用于合成具有不同官能度的七元环。环的形成伴随着1，2-酰氧基迁移事件。环加成反应的5-碳和2-碳组分分别是3-酰氧基-1，4-烯炔（ACEs）和炔。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）配合物可以促进分子间反应。在这两种情况下，缺电子的亚磷酸酯或膦配体通常提高环加成的效率。ACE和炔的范围进行了研究，在分子内和分子间的反应。所得的七元环产物具有三个双键，可以选择性地官能化。
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 5- and 2-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 intra- and intermolecular reactions. The resulting seven-membered ring products have three double bonds that could be selectively functionalized.
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影响因子：
15
作者：
GEMAL, AL;LUCHE, JL
通讯作者：
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通讯作者：
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通讯作者：
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作者：
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通讯作者：
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