Taming Metal/Fluorine Carbenoids
Taming Metal/Fluorine Carbenoids
复制标题
DOI：
10.1002/chem.201605592
复制
发表时间：
2017-02-01
影响因子：
4.3
通讯作者：
Gessner, Viktoria H.
中科院分区：
文献类型：
--
作者：
Molitor, Sebastian;Feichtner, Kai-Stephan;Gessner, Viktoria H.
虽然Li/Cl类碳水化合物是有机合成中用途广泛的试剂，但控制处理极具活性和不稳定性的M/F类碳水化合物仍然是一个挑战。我们现在表明，即使这些化合物也可以在固态和溶液中稳定和分离。特别是钠和钾化合物表现出显著的稳定性，从而首次分离出室温稳定的氟类碳化合物。，以及DFT研究证实了明显的类碳化合物特征，表明M-F-C与延长的C-F键相互作用。发现类碳化合物的不同稳定性源于M-F相互作用的不同强度。因此，锂化合物比它们的重同系物反应性强得多。反应性研究表明，金属的性质也会影响反应性，导致对硫酮的加成选择性不同。
Although Li/Cl carbenoids are versatile reagents in organic synthesis, the controlled handling of the extremely reactive and labile M/F carbenoids remains a challenge. We now show that even these compounds can be stabilized and isolated in solid state, as well as in solution. Particularly the sodium and potassium compounds exhibit a remarkable stability, thus allowing the first isolation of a room-temperature-stable fluorine carbenoid. , as well as DFT studies confirmed the pronounced carbenoid character, showing M-F-C interactions with elongated C-F bonds. The different stabilities of the carbenoids was found to originate from the different strength of the M-F interaction. Hence, the lithium compounds are considerably more reactive than their heavier congeners. Reactivity studies showed that the nature of the metal also influences the reactivity, resulting in different selectivity in the addition to thioketones.