Serendipitous formation of <i>meso</i>-free corroles in the [3+1] porphyrin and [3+2] sapphyrin syntheses
Serendipitous formation of <i>meso</i>-free corroles in the [3+1] porphyrin and [3+2] sapphyrin syntheses
复制标题
[3 1] 卟啉和 [3 2] 蓝宝石合成中偶然形成无<i>内消旋</i>的咔咯
DOI：
10.1142/s1088424622500900
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发表时间：
2023
影响因子：
1.5
通讯作者：
Okujima Tetsuo
中科院分区：
文献类型：
--
作者：
Uno Hidemitsu;Konishi Shota;Nakamura Jun;Mori Shigeki;Takase Masayoshi;Okujima Tetsuo
在基于双环[2.2.2]辛二烯（BCOD）稠合前体的逆狄尔斯-阿尔德反应的制备性研究过程中，通过使用三吡喃-1,14-二甲醛和BCOD稠合吡咯进行[3+1]卟啉合成苯并[]荧蒽[9,10]-[]卟啉，偶然形成观察到相应的响度。阐明反应条件后，[3+1]反应得到21,31-二氢-21,31-乙醇苯并[]荧蒽并[9,10-]咔咯，产率23%以及痕量的相应卟啉。在使用三吡喃-1,14-二甲醛和联吡咯通过[3+2]方法合成蓝宝石中，相似的反应条件导致以38%的产率形成5-吡咯基咔咯以及异麦角烯和最初的目标蓝宝石。
During the preparative investigation of-expanded porphyrinoids based on the retro-Diels-Alder reaction of bicyclo[2.2.2]octadiene(BCOD)-fused precursors for benzo- and benzo[]fluorantho[9,10]-[]porphyrins by the [3+1] porphyrin synthesis using tripyrrane-1,14-dicarbaldehyde and BCOD-fused pyrroles, serendipitous formation of the corresponding corroles was observed. After elucidation of the reaction conditions, the [3+1] reaction afforded 21,31-dihydro-21,31-ethanobenzo[]fluorantho[9,10-]corrole in 23% yield as well as a trace amount of the corresponding porphyrin. In the sapphyrin synthesis by the [3+2] approach using the tripyrrane-1,14-dicarbaldehyde and a bipyrrole, the similar reaction conditions resulted in the formation of 5-pyrrolylcorrole in a 38% yield as well as isosmaragdyrin and the originally targeted sapphyrin.