Molybdenum-Promoted Synthesis of Isoquinuclidines with Bridgehead CF 3 Groups
Molybdenum-Promoted Synthesis of Isoquinuclidines with Bridgehead CF 3 Groups
复制标题
钼促进桥头 CF 3 基团异奎宁环的合成
DOI：
10.1021/jacs.9b10781
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发表时间：
2019
影响因子：
15
通讯作者：
Harman, W. Dean
中科院分区：
文献类型：
--
作者：
Wilde, Justin H.;Smith, Jacob A.;Dickie, Diane A.;Harman, W. Dean
描述了配合物 MoTp(NO)(DMAP)(4,5-η2-(2-三氟甲基)吡啶)（DMAP = 4-(二甲氨基)吡啶；Tp = 三(吡唑基)硼酸盐）的制备。 CF3 取代基被发现可以阻止 κ-N 配位，从而允许在没有氮保护的情况下直接配位。双触配位复合物可以作为单一非对映异构体分离、甲基化并与一系列亲核试剂反应。氧化解络以良好的产率 (75-90%) 提供游离二氢吡啶。作为合成实用性的证明，由这些去络合的二氢吡啶制备了一系列新型桥头CF3取代的异奎宁环。
The preparation of the complex MoTp(NO)(DMAP)(4,5-η2-(2-trifluoromethyl)pyridine) (DMAP = 4-(dimethylamino)pyridine; Tp = tris(pyrazolyl)borate) is described. The CF3substituent is found to preclude κ-N coordination, allowing for direct coordination without protection of the nitrogen. The dihapto-coordinate complex can be isolated as a single diastereomer, methylated, and reacted with a range of nucleophiles. Oxidative decomplexation affords the free dihydropyridines in good yield (75–90%). As a demonstration of synthetic utility, a series of novel bridgehead CF3-substituted isoquinuclidines was prepared from these decomplexed dihydropyridines.