阿佩尔反应_Appel Reaction

阿佩尔反应_Appel Reaction

三苯基膦和四氢甲烷（CCl4，CBr4）与醇的反应是一种在温和条件下将醇转化为相应的卤代烷基的简便方法。产量通常很高。

这种反应有点类似于Mitsunobu反应，其中磷化氢、作为偶联剂的重氮化合物和亲核试剂的组合被用来颠倒或置换醇的立体化学。

Appel反应的机理

该反应通过与四氢甲烷反应活化三苯基膦，然后醇氧在磷上攻击生成氧膦中间体。然后将氧转化成离开基团，并且发生由卤化物引起的SN2位移，如果碳不对称，则进行构型反转。

相关反应

光延反应

斯塔丁格反应

烷基溴的合成

烷基氯化物的合成

Related Reactions

Mitsunobu Reaction

Staudinger Reaction

Synthesis of alkyl bromides

Synthesis of alkyl chlorides

Recent Literature

ROMPgel-Supported Triphenylphosphine with Potential Application in Parallel Synthesis
E. Arstad, A. G. M. Barrett, B. T. Hopkins, J. Koebberling, Org. Lett., 2002, 1975-1977.

Conversion of alcohols to bromides using a fluorous phosphine
L. Desmaris, N. Percina, L. Cottier, D. Sinou, Tetrahedron Lett., 2003, 44, 7589-7591.

Stoichiometric bromotrichloromethane in acetonitrile can replace solvent quantities of carbon tetrachloride in the synthesis of gem-dichloroalkenes from aldehydes in the presence of triphenylphosphine. Similarly, bromotrichloromethane in dichloromethane can be used for the Appel reaction of benzyl alcohols to form benzyl chlorides at r.t., which is commonly carried out in refluxing carbon tetrachloride.
S. G. Newman, C. S. Bryan, D. Perez, M. Lautens, Synthesis, 2011, 342-346.