Joining Hydroxyazobenzene and Mannose under Mitsunobu Conditions

Hain, Julia; Chandrasekaran, Vijayanand

doi:10.1002/ijch.201400211

Cited by 10 publications

(7 citation statements)

References 27 publications

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“…This stereo-differentiating effect of isopropylidene protecting groups was also observed in other cases with D-mannopyranose [ 46 , 61 ]. It might be used as a key to a reliable approach to otherwise difficult to synthesize β-mannosides using the Mitsunobu procedure.…”

Section: Reviewsupporting

confidence: 74%

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Anomeric modification of carbohydrates using the Mitsunobu reaction

Hain¹,

Rollin²,

Klaffke³

et al. 2018

Beilstein J. Org. Chem.

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The Mitsunobu reaction basically consists in the conversion of an alcohol into an ester under inversion of configuration, employing a carboxylic acid and a pair of two auxiliary reagents, mostly triphenylphosphine and a dialkyl azodicarboxylate. This reaction has been frequently used in carbohydrate chemistry for the modification of sugar hydroxy groups. Modification at the anomeric position, leading mainly to anomeric esters or glycosides, is of particular importance in the glycosciences. Therefore, this review focuses on the use of the Mitsunobu reaction for modifications of sugar hemiacetals. Strikingly, unprotected sugars can often be converted regioselectively at the anomeric center, whereas in other cases, the other hydroxy groups in reducing sugars have to be protected to achieve good results in the Mitsunobu procedure. We have reviewed on the one hand the literature on anomeric esterification, including glycosyl phosphates, and on the other hand glycoside synthesis, including S- and N-glycosides. The mechanistic details of the Mitsunobu reaction are discussed as well as this is important to explain and predict the stereoselectivity of anomeric modifications under Mitsunobu conditions. Though the Mitsunobu reaction is often not the first choice for the anomeric modification of carbohydrates, this review shows the high value of the reaction in many different circumstances.

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Section: Reviewsupporting

confidence: 74%

“…Recently, the scope of this synthetic approach was expanded by the Lindhorst group employing D-mannose and hydroxyazobenzene 46 for the synthesis of the photoswitchable azobenzene α-D-mannoside 47 ( Scheme 9 ) [ 46 ]. Notably, in this reaction, traces of an anomeric mixture of the respective furanoside 48 were detected.…”

Section: Reviewmentioning

confidence: 99%

Anomeric modification of carbohydrates using the Mitsunobu reaction

Hain¹,

Rollin²,

Klaffke³

et al. 2018

Beilstein J. Org. Chem.

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“…Thus, a series of hydroxypropylated scaffold glycosides is now available for further functionalization, such as conjugation with thymine or glycothymine derivatives. Moreover, it is advantageous that the oligo‐alcohols obtained in the hydroboration step, can also be addressed with other “switchable” molecules than thymine, such as with hydroxyazobenzene derivatives, serving as the acidic component in a Mitsunobu reaction . We will employ the most useful functional decoration of 2‐NHBoc‐ethyl mannoside in further studies on organization of multivalency.…”

Section: Discussionmentioning

confidence: 99%

Carbohydrate‐Scaffolded Thymine Multimers: Scope and Limitations of the Allylation–Hydroboration Sequence

Ciuk

Gloe

2018

Eur J Org Chem

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Carbohydrates serve as versatile molecular scaffolds and platforms in organic chemistry, for example in combinatorial chemistry or for the multivalent presentation of ligands. Carbohydrate scaffolds are frequently employed in the synthesis of multivalent glycoconjugates and utilized for the study of fundamental parameters of carbohydrate recognition. However, facile procedures are required to achieve a useful variety of sugar platforms. Here, we report on the synthesis of a series of divalent und tetravalent hydroxypropylated mannosides, using an allylation‐hydroboration sequence. The hydroxypropyl‐linkers were further functionalized with thymine in a Mitsunobu reaction to achieve multivalent glycothymine scaffolds for intramolecular [2+2] photocyclization. This will be of importance to further investigate the influence of the 3D orientation in carbohydrate recognition. We discuss the scope of the allylation‐hydroboration sequence comparing 2,3‐, 2,6‐, and 4,6‐difunctionalization and 2,3,4,6‐tetrafunctionalization of protected 2‐aminoethyl α‐d‐mannopyranosides.

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“…Their procedure furnished the desired aryl α-mannopyranoside in moderate yield with slight contamination by an anomeric mixture of mannofuranosides (Scheme 38) [105]. …”

Section: Reviewmentioning

confidence: 99%

“…In 2015 a very similar procedure has been employed for the synthesis of α-mannopyranosyl hydroxyazobenzenes that Lindhorst and colleagues applied to their study of photoswitchable labels. Their procedure furnished the desired aryl α-mannopyranoside in moderate yield with slight contamination by an anomeric mixture of mannofuranosides ( Scheme 38 ) [ 105 ].…”

Section: Reviewmentioning

confidence: 99%

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

Downey

Hocek

2017

Beilstein J. Org. Chem.

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Glycosylation is an immensely important biological process and one that is highly controlled and very efficient in nature. However, in a chemical laboratory the process is much more challenging and usually requires the extensive use of protecting groups to squelch reactivity at undesired reactive moieties. Nonetheless, by taking advantage of the differential reactivity of the anomeric center, a selective activation at this position is possible. As a result, protecting group-free strategies to effect glycosylations are available thanks to the tremendous efforts of many research groups. In this review, we showcase the methods available for the selective activation of the anomeric center on the glycosyl donor and the mechanisms by which the glycosylation reactions take place to illustrate the power these techniques.

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Joining Hydroxyazobenzene and Mannose under Mitsunobu Conditions

Cited by 10 publications

References 27 publications

Anomeric modification of carbohydrates using the Mitsunobu reaction

Anomeric modification of carbohydrates using the Mitsunobu reaction

Carbohydrate‐Scaffolded Thymine Multimers: Scope and Limitations of the Allylation–Hydroboration Sequence

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

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