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Is It Possible to Achieve Organic Superbases beyond the Basicity Limit Using Tetrahedrane Scaffolds?
ChemistrySelect ( IF 1.9 ) Pub Date : 2020-05-20 , DOI: 10.1002/slct.202001407
Younes Valadbeigi 1 , Robert Vianello 2
Affiliation  

Substituted tetrahedranes offer exceptional carbon bases with the gas‐phase proton affinities (PAs) up to 356 kcal mol−1, due to the strain‐induced ring opening upon protonation. Additional tetrahedrane moieties exert a dramatic basicity amplification to PAs reaching 600 kcal mol−1, being the strongest organic superbases reported, clearly surpassing the proposed limit of achievable basicities (Angew. Chem. Int. Ed. 2015, 54, 9262). However, because protonation/deprotonation of these compounds is not reversible, PAs of the opened‐cage isomers were calculated which were lower than the basiciy limit.

中文翻译:

使用四面体支架能否获得超出碱性极限的有机超碱?

取代的四面体提供了优异的碳碱,其气相质子亲和力(PAs)高达356 kcal mol -1,这是由于在质子化过程中应变引起的开环。另外的四面戊二烯部分对PAs起到了戏剧性的碱性增强作用,达到600 kcal mol -1,是所报道的最强的有机超强碱,明显超过了建议的可达到的碱性极限(Angew。Chem。Int。Ed。2015,54,9262)。但是,由于这些化合物的质子化/去质子化是不可逆的,因此计算出的开式异构体的PA低于基本限值。
更新日期:2020-05-20
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