Bentabed-Ababsa Ghenia, Derdour Aicha, Roisnel Thierry, Sáez Jose A, Domingo Luis R, Mongin Florence
Chimie et Photonique Moléculaires, UMR 6510 CNRS, Université de Rennes 1, Bâtiment 10A, Case 1003, Campus Scientifique de Beaulieu, F-35042, Rennes Cedex, France.
Org Biomol Chem. 2008 Sep 7;6(17):3144-57. doi: 10.1039/b804856h. Epub 2008 Jul 3.
The [3 + 2] cycloaddition reaction between carbonyl ylides generated from epoxides and ketones (ethyl pyruvate, ethyl phenylglyoxylate, isatin, N-methylisatin and 5-chloroisatin) to give substituted dioxolanes and spirocyclic dioxolane indolinones was investigated. The effect of microwave irradiation on the outcome of the reaction was studied. The thermal reaction between 2,2-dicyano-3-phenyloxirane and N-methylisatin was theoretically studied using DFT methods. This reaction is a domino process that comprises two steps. The first is the thermal ring opening of the epoxide to yield a carbonyl ylide intermediate, whereas the second step is a polar [3 + 2] cycloaddition to yield the final spiro cycloadducts. The cycloaddition presents a low stereoselectivity and a large regio- and chemoselectivity. Analysis of the electrophilicity values and the Fukui functions of the reagents involved in the cycloaddition step allowed the chemical outcome to be explained.
研究了由环氧化物与酮（丙酮酸乙酯、苯乙醛酸乙酯、异吲哚酮、N-甲基异吲哚酮和5-氯异吲哚酮）生成的羰基叶立德之间的[3 + 2]环加成反应，以得到取代的二氧戊环和螺环二氧戊环吲哚酮。研究了微波辐射对反应结果的影响。使用密度泛函理论（DFT）方法从理论上研究了2,2-二氰基-3-苯基环氧乙烷与N-甲基异吲哚酮之间的热反应。该反应是一个多米诺过程，包括两个步骤。第一步是环氧化物的热开环生成羰基叶立德中间体，而第二步是极性[3 + 2]环加成生成最终的螺环环加成产物。该环加成反应具有较低的立体选择性以及较大的区域选择性和化学选择性。对环加成步骤中涉及的试剂的亲电值和福井函数进行分析，可以解释化学反应结果。
