Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
Metal-Free Arylation of Oxygen Nucleophiles with Diaryliodonium Salts
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DOI：
10.1002/chem.201201645
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发表时间：
2012-10-01
影响因子：
4.3
通讯作者：
Olofsson, Berit
中科院分区：
文献类型：
--
作者：
Jalalian, Nazli;Petersen, Tue B.;Olofsson, Berit
酚和羧酸被二芳基碘鎓盐有效地芳基化。反应条件温和，不含金属，避免使用卤化溶剂，添加剂和过量试剂。在短的反应时间后以良好至优异的产率获得产物。在亲核试剂和二芳基碘鎓盐中，空间位阻是非常好地耐受的。范围包括邻位和卤素取代的产品，这是很难获得的金属催化的协议。许多官能团是容许的，包括羰基、杂原子和烯烃。不对称盐可以化学选择性地用于获得具有迄今未报道的空间拥挤水平的产物。芳基化已经扩展到磺酸，其可以通过两种不同的方法转化为磺酸酯。随着二芳基碘鎓盐的有效合成方法的最新进展，试剂现在便宜且容易获得。由碘鎓试剂形成的碘代芳烃副产物可以定量回收并用于再生二芳基碘鎓盐，这提高了原子经济性。
Phenols and carboxylic acids are efficiently arylated with diaryliodonium salts. The reaction conditions are mild, metal free, and avoid the use of halogenated solvents, additives, and excess reagents. The products are obtained in good-to-excellent yields after short reaction times. Steric hindrance is very well tolerated, both in the nucleophile and diaryliodonium salt. The scope includes ortho-and halo-substituted products, which are difficult to obtain by metal-catalyzed protocols. Many functional groups are tolerated, including carbonyl groups, heteroatoms, and alkenes. Unsymmetric salts can be chemoselectively utilized to obtain products with hitherto unreported levels of steric congestion. The arylation has been extended to sulfonic acids, which can be converted to sulfonate esters by two different approaches. With recent advances in efficient synthetic procedures for diaryliodonium salts the reagents are now inexpensive and readily available. The iodoarene byproduct formed from the iodonium reagent can be recovered quantitatively and used to regenerate the diaryliodonium salt, which improves the atom economy.