DEVELOPMENT OF HIGHLY EFFICIENT BENZYNE TRANSFORMATION PROCESS USING HYPERVALENT IODINE COMPOUNDS

我们合成了一种新型的高价碘试剂--[邻三甲基硅基]苯基三氟化碘，它带有一个高左旋的苯基和一个易裂解的硅基，并发展了一种高效的苯炔转化过程：(1)用我们开发的高活性高价碘试剂制备了苯炔前体[邻三甲基硅基]三氟化碘。(2)在非常温和的条件下，用Bu4Nf和KF可以很容易地原位生成苯炔。(3)用呋喃、异苯并呋喃、菲、环戊二酮等定量捕获生成的苯炔。由于该试剂可以在中性条件下和常温下使用，因此可以应用于不稳定的叠氮化合物和硫代二苯甲酮的反应。(5)制备取代苯炔前驱体，并对其进行了研究。

We have prepared a new type of hypervalent iodine reagent, [o-(trimethylsilyl) phenyl] iodonium triflates, which bear a hyperleaving phenyliodonio group and a readily cleavable silyl group, and developed a highly efficient benzyne transformation process.(1) The benzyne precursor, [o-(trimethylsilyl) phenyl] iodonium triflate, was prepared by using highly reactive hypervalent iodine reagents developed by us.(2) Benzyne was readily generated in situ under very mild conditions by using Bu_4NF and KF.(3) The generated benzyne as above was quantitatively trapped by furan, isobenzofuran, anthracene, cyclopentadienone, and so on. This reaction provides a highly efficient benzyne transformation process.(4) Since the present reagent can be utilized under neutral conditions and at room temperature, it can be applied to the reactions with unstable azides and thiobenzophenones.(5) Substituted benzyne precursors were prepared and investigated in order to find the utility.