Gao Guang-Yao, Colvin Andrew J, Chen Ying, Zhang X Peter
Department of Chemistry, University of Tennessee, Knoxville, Tennessee 37996-1600, USA.
Org Lett. 2003 Sep 4;5(18):3261-4. doi: 10.1021/ol035081t.
[reaction: see text] meso-Aryloxy- and alkoxy-substituted porphyrins were conveniently synthesized by direct reactions of meso-halogenated porphyrins with alcohols via palladium-catalyzed C-O cross-coupling reactions. Using a combination of palladium precursor Pd(OAc)(2) or Pd(2)(dba)(3) and phosphine ligand DPEphos or Xantphos allowed both 5-bromo-10,20-diarylporphyrin and 5,15-dibromo-10,20-diarylporphyrin, as well as their zinc complexes, to be effectively coupled with a variety of alcohols to give the corresponding mono- and bis-substituted meso-aryloxy/alkoxyporphyrins in moderate to high yields under mild conditions.
[反应：见正文] 通过中卤代卟啉与醇类经钯催化的C-O交叉偶联反应直接反应，可方便地合成中位芳氧基和烷氧基取代的卟啉。使用钯前体Pd(OAc)₂或Pd₂(dba)₃与膦配体DPEphos或Xantphos的组合，5-溴-10,20-二芳基卟啉和5,15-二溴-10,20-二芳基卟啉及其锌配合物，均能与多种醇类有效偶联，在温和条件下以中等到高的产率得到相应的单取代和双取代中位芳氧基/烷氧基卟啉。
