MECHANISTIC INVESTIGATION OF THE COPPER-CATALYZED REACTIONS OF DIPHENYLIODONIUM SALTS
MECHANISTIC INVESTIGATION OF THE COPPER-CATALYZED REACTIONS OF DIPHENYLIODONIUM SALTS
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DOI：
10.1021/ja00345a045
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发表时间：
1983-01-01
影响因子：
15
通讯作者：
LOCKHART, TP
中科院分区：
文献类型：
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作者：
LOCKHART, TP
六氟砷酸二苯碘鎓盐（PIFA）与苯甲酸铜（II）在乙醇溶剂中反应，沿着少量苯甲酸苯酯和苯，以高产率得到碘苯和芳基化产物烷基苯基醚。使用二苯基碘溴化铵（PIBr），与碘苯和醚一起得到沿着大量的溴苯。在非亲核溶剂CH_2Cl_2中，PIFA生成大量的碘苯、苯、联苯和苯甲酸苯酯。在CH_2Cl_2中，PIBr得到高收率的溴苯和碘苯以及低收率的苯和联苯。Cu1被证明是铜的催化活性氧化态，部分基于用独立制备的苯甲酸铜（I）观察到的化学。苯基自由基中间体被排除在PIFA和PIBr在甲醇和CH2Cl2中的反应中，并且它们的化学性质与用重氮苯盐观察到的化学性质形成对比。一个机制，涉及苯基铜（III）的中间体，提出了简洁的帐户与PIFA和PIBr在亲核和nonnucleophilic溶剂中观察到的反应产物。
The reaction of diphenyliodonium hexafluoroarsenate (PIFA) with copper (II) benzoate in alcohol solvent gives iodobenzene and alkyl phenylether, the arylation product, in high yield along with smallamounts of phenyl benzoate and benzene. With diphenyliodonium bromide (PIBr), a substantial yield of bromobenzene is obtained along with iodobenzene and the ether. In nonnucleophilicsolvent, CH2C12, PIFA yields appreciable amounts of iodobenzene, benzene, biphenyl, and phenyl benzoate. In CH2C12, PIBr gives a high yield of bromobenzene and iodobenzene and low yields of benzene and biphenyl. Cu1 isshown to be the catalytically active oxidation state of copper, based in part on the chemistry observed with independently prepared copper (I) benzoate. Phenyl radical intermediates are ruled out in the reactions of PIFA and PIBr in methanol and CH2C12, and their chemistry is contrasted with that observed with a benzenediazonium salt. A mechanism involving a phenylcopper (III) intermediate is proposed which concisely accounts for the reaction products observed with PIFA and PIBr in both nucleophilic and nonnucleophilic solvents.