Is It Possible to Achieve Organic Superbases beyond the Basicity Limit Using Tetrahedrane Scaffolds?

被引：11

作者：

Valadbeigi, Younes ^{[1
]}

Vianello, Robert ^{[2
]}

机构：

[1] Imam Khomeini Int Univ, Fac Sci, Dept Chem, POB 288, Qazvin, Iran

[2] Rudjer Boskovic Inst, Div Organ Chem & Biochem, Computat Organ Chem & Biochem Grp, Bijenicka Cesta 54, Zagreb 10002, Croatia

来源：

CHEMISTRYSELECT | 2020年 / 5卷 / 19期

关键词：

Basicity; Density Functional Calculations; Structural Strain; Tetrahedrane; GAS-PHASE; PROTON AFFINITIES; RING STRAIN; AB-INITIO; DESIGN; ORGANOSUPERBASES; HETEROCYCLES; MOLECULES; OXYGEN; CUBANE;

D O I：

10.1002/slct.202001407

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

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.

引用

页码：5794 / 5798

页数：5

共 2 条

[1] Kinetics screening of the N-alkylation of organic superbases using a continuous flow microfluidic device: basicity versus nucleophilicity
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[2] Optimizing the Charge Balance of Fluorescent Organic Light-Emitting Devices to Achieve High External Quantum Efficiency Beyond the Conventional Upper Limit
Pu, Yong-Jin
Nakata, Go
Satoh, Fumiya
Sasabe, Hisahiro
Yokoyama, Daisuke
Kido, Junji
ADVANCED MATERIALS, 2012, 24 (13) : 1765 - 1770

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