Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides,Organic Chemistry Frontiers

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Tunable regiodivergent phosphine-catalyzed [3 + 2] cycloaddition of alkynones and trifluoroacetyl phenylamides
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2017-08-29 00:00:00 , DOI: 10.1039/c7qo00512a
Yao-Liang Sun _{1,

2,

3,

4,

5} , Yin Wei _{6,

7,

8,

9,

10} , Min Shi _{1,

2,

3,

4,

5}

Affiliation

Alkynones can be activated by phosphine as a nucleophilic catalyst, and then trapped by a series of trifluoroacetyl phenylamides to afford cycloaddition products. Through subtly adjusting the substituent of trifluoroacetyl phenylamides, the addition of water and changing the reaction temperature, two kinds of highly regioselective cycloaddition products were obtained in moderate to excellent yields. Plausible mechanisms were proposed and supported by the deuterium-labeling experiments and DFT calculations. DFT calculations demonstrate that the currently accepted intramolecular proton transfer processes involved in these reactions are impossible, and these proton transfer processes can proceed with the assistance of substrates containing an acidic moiety or by the addition of water. Our mechanistic studies provide reasonable explanations for the regioselectivity affected by the protic additive H₂O, and the reaction temperature.

中文翻译：

可调谐的区域发散性膦催化炔烃和三氟乙酰基苯基酰胺的[3 + 2]环加成

炔烃可以通过膦作为亲核催化剂活化，然后被一系列三氟乙酰基苯基酰胺捕获，得到环加成产物。通过巧妙地调节三氟乙酰基苯基酰胺的取代基，添加水和改变反应温度，以中等至极好的收率获得了两种高度区域选择性的环加成产物。氘标记实验和DFT计算提出了合理的机制并提供了支持。DFT计算表明，这些反应中目前公认的分子内质子转移过程是不可能的，并且这些质子转移过程可以在含有酸性部分的底物的帮助下或通过添加水而进行。₂ O，与反应温度有关。

更新日期：2017-09-12

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