Stereoselective one-pot sequential dehydrochlorination/trans-hydrofluorination reaction of β-chloro-α,β-unsaturated aldehydes or ketones: facile access to (Z)-β-fluoro-β-arylenals/β-fluoro-β-arylenones
Stereoselective one-pot sequential dehydrochlorination/trans-hydrofluorination reaction of β-chloro-α,β-unsaturated aldehydes or ketones: facile access to (Z)-β-fluoro-β-arylenals/β-fluoro-β-arylenones
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b-氯-a,b-不饱和醛或酮的立体选择性一锅顺序脱氯化氢/反式氢氟化反应：轻松获得(Z)-b-氟-b-芳醛/b-氟-b-亚芳酮
DOI：
10.1002/adsc.201700981
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发表时间：
2017
影响因子：
5.4
通讯作者：
Yuefa Gong
中科院分区：
文献类型：
--
作者：
Jingli Zhang;Liran Liu;Junxin Duan;Lianghu Gu;Bifeng Chen;Taolei Sun;Yuefa Gong
单氟烯烃亚结构在有机合成中显示出作为氟化合成子的高潜力。然而，在一锅法反应中控制多取代单氟烯烃产物的Z/E立体选择性仍然是一个挑战。探索了一种前所未有的从容易获得的b-氯-a，b-不饱和醛或酮高度区域选择性和立体选择性地制备官能化（Z）-b-单氟三取代烯烃的一锅法。机理研究表明，该反应是由底物脱氯化氢得到炔基醛/酮，然后由它们的反式加氢引发的。值得一提的是，具有合适的碱性和亲核性的氟化试剂在促进（Z）-b氟-b-芳基三取代单氟烯烃的形成中起关键作用。
The monofluoroalkene substructure shows a high potential as a fluorinated synthon in organic synthesis. However, control of the Z/E stereoselectivity of multi-substituted monofluoroalkene products in one-pot reactions still remains a challenge. An unprecedented one-pot approach for the highly regio- and stereoselective preparation of functionalized (Z)-b-monofluoro tri-substituted alkenes from readily available b-chloro-a,b-unsaturated aldehydes or ketones has been explored. Mechanistic studies demonstrated that the reaction is initiated by dehydrochlorination of the substrates to give alkynyl aldehydes/ketones, followed by their trans-hydrofluorination. It is worth mentioning that a fluorinating reagent with suitable basicity and nucleophilicity plays a key role in promoting the formation of (Z)-bfluoro-b-aryl tri-substituted monofluoroalkenes..