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本文报道仲酰胺经去胺基烷基化反应直接合成酮的通用性方法.这一新的C—C键形成方法是基于Tf2O对仲酰胺的活化及有机铈试剂对活化所形成活性中间体的加成而实现的.该方法可用于各种酮的合成,包括烷基-烷基酮、烷基-芳基酮、芳基-芳基酮、α,β-不饱和酮以及β-氯-α,β-不饱和酮等,收率65%～90%.研究表明,除了有机铈试剂外,碱性较弱的炔基硼试剂、温和亲核性的烯丙基三甲基硅烷以及低亲核性的苯乙烯均可与仲酰胺的活化中间体进行加成反应,水解后生成相应的酮.因此,该方法具有较好的普适性和重要的合成应用价值.基于实验结果和验证实验,提出经由腈鎓中间体的可能反应机理.本法使仲酰胺成为形式上的酰化试剂,不但可与有机金属试剂反应,还可与烯丙基三甲基硅烷和苯乙烯进行还原酰化反应.
In this paper, a general method for the direct synthesis of ketones from secondary amides via deamination of alkylamines is reported. The new C-C bond formation method is based on the activation of secondary amides by Tf2O and the activity of organic cerium reagents on the activation of active intermediates The method is useful for the synthesis of various ketones including alkyl-alkyl ketones, alkyl-aryl ketones, aryl-aryl ketones, [alpha], [beta] -unsaturated ketones and [beta] α, β-unsaturated ketone, etc., yield 65% to 90% .Studies show that, in addition to the organic cerium reagent, alkyne boron reagent weak base, mild nucleophilic allyltrimethylsilane and low The nucleophilic styrene can be added with the secondary amide activation intermediates to generate the corresponding ketone after hydrolysis.Therefore, this method has good universality and important synthetic value.According to the experimental results and verification Experiments suggest a possible reaction mechanism via the nitrileium intermediates.This method to form a secondary amide acylation reagent, not only with organic metal reagents, but also with allyl trimethylsilane and styrene reductive acylation The reaction.