A compatibility study on the glycosylation of 4,4′-dihydroxyazobenzene

Berry, Jonathan; Despras, Guillaume

doi:10.1039/d0ra02435j

Cited by 9 publications

(15 citation statements)

References 53 publications

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“…Azobenzene‐modified glycoconjugates have been widely used in the field of biochemistry, [ 262 ] and they also show potential utility in studying the interactions between carbohydrates and proteins. [ 263 ] Carbohydrate derivatives (for example, pyranose derivatives) are building blocks that have a good biocompatibility and a high degree of functional and structural diversity. Therefore, the presence of sugar units in the macrocycle makes it possible to regulate the physical and chemical properties of the entire ring system.…”

Section: Main Specific Applications Of Azobenzenementioning

confidence: 99%

“…Therefore, the presence of sugar units in the macrocycle makes it possible to regulate the physical and chemical properties of the entire ring system. [ 264 ] The glycosylation of azobenzene derivatives (e.g., 4,4′‐dihydroxyazobenzene (DHAB) [ 263 ] ) is usually the first critical step to consider when constructing a photoresponsive macromolecular system. [ 265 ] DHAB is not a very active glycosyl acceptor because tautomerism between the quinone and phenol form leads to a decrease in nucleophilicity of phenolic hydroxy groups.…”

Section: Main Specific Applications Of Azobenzenementioning

confidence: 99%

“…Protecting groups, changes to 6‐position functional group and fine‐tuning of reaction conditions all improve the stereoselectivity and degree of substitution. [ 263 ]…”

Section: Main Specific Applications Of Azobenzenementioning

confidence: 99%

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Advances in Application of Azobenzene as a Trigger in Biomedicine: Molecular Design and Spontaneous Assembly

et al. 2021

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Azobenzene is a well‐known derivative of stimulus‐responsive molecular switches and has shown superior performance as a functional material in biomedical applications. The results of multiple studies have led to the development of light/hypoxia‐responsive azobenzene for biomedical use. In recent years, long‐wavelength‐responsive azobenzene has been developed. Matching the longer wavelength absorption and hypoxia‐response characteristics of the azobenzene switch unit to the bio‐optical window results in a large and effective stimulus response. In addition, azobenzene has been used as a hypoxia‐sensitive connector via biological cleavage under appropriate stimulus conditions. This has resulted in on/off state switching of properties such as pharmacology and fluorescence activity. Herein, recent advances in the design and fabrication of azobenzene as a trigger in biomedicine are summarized.

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Section: Main Specific Applications Of Azobenzenementioning

confidence: 99%

Section: Main Specific Applications Of Azobenzenementioning

confidence: 99%

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Advances in Application of Azobenzene as a Trigger in Biomedicine: Molecular Design and Spontaneous Assembly

et al. 2021

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“…Therefore, we have recently investigated this reaction in detail and concluded that the scope of glycosyl donors and activation methods is very limited. [13] Likewise, the use of the Mitsunobu reaction for the conjugation of DHAB to the anomeric center or primary positions of glycosides was highly substrate-dependent and often led to low to moderate yields. [13] In view of the contrasting results obtained with the aforementioned methods, we sought for a reliable conjugation reaction effective on a wide scope of substrates, also including more sophisticated azoswitches such as ortho-substituted azobenzenes [15] and diazocine, an orthoethylene bridged azobenzene.…”

Section: Introductionmentioning

confidence: 99%

Sulfur and Azobenzenes, a Profitable Liaison: Straightforward Synthesis of Photoswitchable Thioglycosides with Tunable Properties

Berry

Despras

2022

Chemistry A European J

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Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. We have been investigating azobenzene glycoconjugates to probe carbohydrate-protein interactions and to design glycoazobenzene macrocycles with chiroptical and physicochemical properties modulated by light irradiation. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiols, thereby increasing the scope of azobenzene conjugation. Even challenging unsymmetrical conjugates can be achieved in good yields via sequential or one-pot procedures. Importantly, red-shifted azoswitches, which are addressed with visible light, were easily functionalized. Additionally, by oxidation of the sulfide bridge to the respective sulfones, both the photochromic and the thermal relaxation properties of the core azobenzene can be tuned. Utilizing this option, we realized orthogonal three-state photoswitching in mixtures containing two distinct azobenzene thioglycosides.

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“…We investigated recently this reaction in detail and concluded that the scope of glycosyl donors and activation methods is very limited. 12 As well, the use of Mitsunobu reaction for the conjugation of DHAB to the anomeric centre or primary positions of glycosides was highly substrate-dependent and often led to low to moderate yields. 13b In view of the contrasted results obtained with the aforementioned methods, we sought for a reliable conjugation reaction effective on a wide scope of substrates, also including more sophisticated azoswitches such as ortho-substituted azobenzenes 14 and diazocine, an ortho-ethylene bridged azobenzene.…”

Section: Introductionmentioning

confidence: 99%

Sulfur and azobenzenes, a profitable liaison: straightforward synthesis of photoswitchable thioglycosides with tunable properties

Berry

Despras

2021

Preprint

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Azobenzene photoswitches are valuable tools for controlling properties of molecular systems with light. In particular, we have been investigating azobenzene glycoconjugates to probe carbohydrate-protein interactions and also to design photoresponsive glycomacrocycles with modulable chiroptical and physicochemical properties. To date, direct conjugation of glycosides to azobenzenes was performed by reactions providing target compounds in limited yields. We therefore sought for a more effective and reliable coupling method. In this paper, we report on a straightforward thioarylation of azobenzene derivatives with glycosyl thiols as well as other thiol substrates, increasing the scope of azobenzene conjugation. Importantly, red-shifted azoswitches that can be addressed with visible light were easily functionalized and challenging unsymmetrical conjugates were prepared in good yields via sequential or one pot procedures. In addition, we took advantage of the presence of the sulfide bridge to tune both photochromic and thermal relaxation properties of the core azobenzene via sulfur oxidation. Based on our photochemical investigations, we finally demonstrated orthogonal three-state photoswitching in mixtures containing two distinct azobenzene thioglycosides.

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A compatibility study on the glycosylation of 4,4′-dihydroxyazobenzene

Abstract: The glycosylation of 4,4′-dihydroxyazobenzene was investigated to identify suitable conditions providing access to valuable photoswitchable glycoconjugates.

Cited by 9 publications

References 53 publications

Advances in Application of Azobenzene as a Trigger in Biomedicine: Molecular Design and Spontaneous Assembly

Advances in Application of Azobenzene as a Trigger in Biomedicine: Molecular Design and Spontaneous Assembly

Sulfur and Azobenzenes, a Profitable Liaison: Straightforward Synthesis of Photoswitchable Thioglycosides with Tunable Properties

Sulfur and azobenzenes, a profitable liaison: straightforward synthesis of photoswitchable thioglycosides with tunable properties

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