<i>ortho</i>-C–H Acetoxylation of Cubane Enabling Access to Cubane Analogues of Pharmaceutically Relevant Scaffolds

Nagasawa, Sumio; Hosaka, Mamoru; Iwabuchi, Yoshiharu

doi:10.1021/acs.orglett.1c03144

Cited by 14 publications

(7 citation statements)

References 58 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…When a silyl ether, a protected amino group or a hydrogen atom is present at the C‐4 position, the reaction is messy. This method is a good method to access trisubstituted cubanes if a cyano or an amido group is present at the C‐4 position [71] ( Scheme 44).…”

Section: Formation Of C−o Bondsmentioning

confidence: 99%

Functionalization of Cubane Formation of C−C and C−Heteroatom Bonds

Yasukawa,

Håheim,

Cossy

2024

Helvetica Chimica Acta

View full text Add to dashboard Cite

Functionalized cubanes are attractive scaffolds for medicinal chemists as they are bioisosteres of benzene rings. The replacement of a benzene ring by a cubane, in a bioactive compound, can have a beneficial effect on the biological activity of such compound. Thus, the design of new molecular cubyl building blocks is of importance. In this review, we will focus on the functionalization of cubanes by creating C−C, C−heteroatom bonds e. g. C−N, C−O, C−B, C−P and C−S bonds. Different methods are reported involving organometallics, radicals, and ionic species. Mechanisms are included when relevant.

show abstract

Section: Formation Of C−o Bondsmentioning

confidence: 99%

Functionalization of Cubane Formation of C−C and C−Heteroatom Bonds

Yasukawa,

Håheim,

Cossy

2024

Helvetica Chimica Acta

View full text Add to dashboard Cite

show abstract

“…Treatment of 24 with a Pd catalyst and an oxidizing reagent produced a mixture of α-mono- and α,α′-diacetoxylated products 25a and 25b . 19b…”

Section: Functionalization Of Cubanementioning

confidence: 99%

Decoration on Cubane with an Awareness of Chirality: Development of Substituted Cubane Syntheses

Takebe

Matsubara

2023

Synthesis

View full text Add to dashboard Cite

Nearly 60 years have passed since Professor Eaton's practical synthesis of cubane, and research using it as a unique molecular scaffold has since gained momentum. Since the early synthesis of polynitrocubane, it's been shown that up to eight substituents can be covalently assembled into a confined space. The arrangement of substituents on a cubane has paved the way for the creation of unique asymmetric molecules. To put it another way, chirality is manifested by selectively introducing three or more diverse types of substituents at specific sites. Recently, there's also been a report on the synthesis of perfluorocubane, a molecule with intriguing electronic properties. 1. Introduction 2. General Information 3. Functionalization of cubane 4. Preparation of poly-substituted cubanes 5. Conclusion

show abstract

“…The extremely strained yet remarkably stable cubane system has been attracting unflagging scientific attention , since its planful synthesis in 1964. − Some of its potential applications include pharmaceuticals (a rigid cubane cage is considered a phenyl bioisoster), − fuels, explosives, , building blocks in material chemistry, , etc. The recently published decagram synthesis of one of the key building blocks, dimethyl cubane-1,4-dicarboxylate, in combination with the rapid development of new chemical tools allowing the functionalization of its scaffold , clearly indicates that the synthesis of cubane derivatives has not reached its end yet.…”

Section: Introductionmentioning

confidence: 99%

Chlorinated Cubane-1,4-dicarboxylic Acids

et al. 2023

View full text Add to dashboard Cite

Herein, we report radical chlorination of cubane-1,4-dicarboxylic acid leading preferentially to one monochlorinated cubane dicarboxylate (ca. 70%) that is accompanied by four dichlorinated derivatives (ca. 20% in total). The exact positions of the chlorine atoms have been confirmed by X-ray diffraction of the corresponding single crystals. The acidity constants of all dicarboxylic acids in water were determined by capillary electrophoresis (3.17 ± 0.04 and 4.09 ± 0.05 for monochlorinated and ca. 2.71 ± 0.05 and 3.75 ± 0.05 for dichlorinated cubanes). All chlorinated derivatives as well as the parent diacid showed high thermal stability (decomposition above 250 °C) as documented by differential scanning calorimetry. The probable reaction pathways leading to individual isomers were proposed, and the energies of individual transition states and intermediates were obtained using density functional theory calculations (B3LYP-D3BJ/6-311+G(d,p)). The relative strain energies for all newly prepared derivatives as well as for hypothetical hexahalogenated (fluorinated, chlorinated, brominated, and iodinated) derivatives of cubane-1,4-dicarboxylic acids were predicted using wavefunction theory methods. The hexafluorinated derivative was identified as the most strained compound (57.5 kcal/mol), and the relative strain decreased as the size of halogen atoms increased (23.7 for hexachloro, 16.7 for hexabromo, and 4.0 kcal/mol for the hexaiodo derivative).

show abstract

ortho-C–H Acetoxylation of Cubane Enabling Access to Cubane Analogues of Pharmaceutically Relevant Scaffolds

Cited by 14 publications

References 58 publications

Functionalization of Cubane Formation of C−C and C−Heteroatom Bonds

Functionalization of Cubane Formation of C−C and C−Heteroatom Bonds

Decoration on Cubane with an Awareness of Chirality: Development of Substituted Cubane Syntheses

Chlorinated Cubane-1,4-dicarboxylic Acids

Contact Info

Product

Resources

About