Liu Xin, Sternberg Ethan, Dolphin David
Department of Chemistry, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1, Canada.
J Org Chem. 2008 Sep 5;73(17):6542-50. doi: 10.1021/jo8007989. Epub 2008 Aug 2.
To find a general strategy for modifying the peripheral structure of vinylchlorin and porphyrin substrates, cross-metathesis on the vinyl group of these tetrapyrrolic macrocycles was investigated. The N-heterocyclic carbene-containing ruthenium complex 3 efficiently catalyzed the cross-metathesis (CM) of vinylchlorins and vinylporphyrins with a variety of olefins in high E-stereoselectivity. Different substituents on the olefin dramatically influenced the reaction. While the chlorins were more reactive than the porphyrins (as free bases), the corresponding zinc complexes showed higher activity. The reaction mechanism was investigated, and an empirical model for selective CM was applied to our studies to direct further reactions.
为了找到一种修饰乙烯基二氢卟吩和卟啉底物外围结构的通用策略，对这些四吡咯大环化合物乙烯基上的交叉复分解反应进行了研究。含氮杂环卡宾的钌配合物3能高效催化乙烯基二氢卟吩和乙烯基卟啉与多种烯烃的交叉复分解反应（CM），具有较高的E-立体选择性。烯烃上不同的取代基对反应有显著影响。虽然二氢卟吩（作为游离碱）比卟啉更具反应活性，但相应的锌配合物表现出更高的活性。对反应机理进行了研究，并将选择性CM的经验模型应用于我们的研究中以指导进一步的反应。
