有机人名反应Vilsmeier-Haack 甲酰化反应.pptVIP

VILSMEIER-HAACK FORMYLATION 维尔斯迈尔－哈克反应 Vilsmeier-Haack reaction 维尔斯迈尔－哈克反应（Vilsmeier-Haack reaction）是指芳香化合物与二取代甲酰胺在三氯氧磷作用下，反应生成芳环上甲酰化产物[1]。该反应只适于活泼底物，如苯酚、苯胺。 Vilsmeier-Haack reaction Vilsmeier-Haack reaction 反应机理 1.维尔斯迈尔－哈克甲酰化反应也可在缩醛的α-位上进行，水解后得到β-醛酮或者β-二醛[3]。 2.烯烃也可以与DMF/POCl3体系进行同样的甲酰化反应，称为维尔斯迈尔反应（Vilsmeier reaction）。 3.酮与DMF/POCl3体系反应，得到β-氯代烯醛，称为维尔斯迈尔－哈克－阿诺德反应（Vilsmeier-Haack-Arnold reaction） Vilsmeier-Haack reaction Mechanism: Vilsmeier-Haack reaction Synthetic Applications: 1 The total synthesis of the calophylium coumarin (–)-calanolide A was accomplished by D.C. Baker and co-workers.43 This compound attracted considerable attention because it is a potent inhibitor of HIV-1 reverse transcriptase. In order to introduce a formyl group at C8, a regioselective Vilsmeier reaction was employed on a coumarin lactone substrate. Vilsmeier-Haack reaction In the laboratory of F.E. Ziegler, the cyclization of a chiral aziridinyl radical into an indole nucleus was utilized to prepare the core nucleus of the potent antitumor agent FR-900482.44 In the early stages of the synthetic effort, the Vilsmeier-Haack formylation was chosen to install an aldehyde functionality at the C3 position of a substituted indole substrate. The initial iminium salt was hydrolyzed under very mildly basic conditions to minimize the hydrolysis of the methyl ester moiety. Eventually the formyl group was removed from the molecule via decarbonylation using Wilkinsons catalyst. Vilsmeier-Haack reaction The total synthesis of (–)-(R)-MEM-protected arthrographol was accomplished by G.L.D. Krupadanam et al.47 The authors used sequential Vilsmeier reaction/Dakin oxidation to prepare a 1,2,4-trihydroxybenzene derivative. Vilsmeier-Haack reaction Now The application of Vilsmeier-Haack reaction in the synthesis of the agrochemicals such as fenpyroximate，imazaquin，furametpyr was reviewed Vilsmeier-Haack reaction Vilsmeier-Haack reaction 1? Vilsmeier,A.and Haack,A.Ber.1937,60,119. 2 Cam