All That metas─Synthesis of Dispersion Energy Donor-Substituted Benzenes.
All That metas─Synthesis of Dispersion Energy Donor-Substituted Benzenes.
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DOI：
10.1021/acs.orglett.2c02780
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发表时间：
2022-09
期刊：
影响因子：
5.2
通讯作者：
Lukas Ochmann;Michael Fuhrmann;Felix J Gössl;Alexander Makaveev;P. Schreiner
中科院分区：
文献类型：
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作者：
Lukas Ochmann;Michael Fuhrmann;Felix J Gössl;Alexander Makaveev;P. Schreiner
我们报告了一种从容易获得的 3,5-二取代儿茶酚合成全间位三取代苯的通用且可扩展的方法。与乙炔亲双烯体的氧化和[4 + 2]环加成反应生成双环[2.2.2]辛烷结构，该结构由蓝光照射引发双重脱羰，从而在重新芳构化系统上产生间位、间位双取代模式。这使得即使具有非常大的烷基基团（被认为是优异的分散能量供体）的这种取代模式也能够被引入到例如手性磷酸催化剂中。
We report a general and scalable method for the synthesis of all-meta-trisubstituted benzenes from readily available 3,5-disubstituted catechols. Oxidation and [4 + 2] cycloaddition with acetylene dienophiles generate a bicyclo[2.2.2]octane structure that is doubly decarbonylated initiated by blue-light irradiation, leading to a meta,meta-disubstitution pattern on the re-aromatized system. This enables this substitution pattern even with very bulky alkyl groups (deemed excellent dispersion energy donors) to be incorporated into, for example, chiral phosphoric acid catalysts.