ChemInform Abstract: Dimethyltin Dichloride Catalyzed Regioselective Alkylation of cis‐1,2‐Diols at Room Temperature.

Carbohydrates are a fundamental unit playing pivotal roles in all the biological processes. It is thus essential to develop methods for synthesizing, functionalizing, and manipulating carbohydrates for further understanding of their functions and the creation of sugar-based functional materials. It is, however, not trivial to develop such methods, since carbohydrates are densely decorated with polar and similarly reactive hydroxy groups in a stereodefined manner. New approaches to chemo-and site-selective transformations of carbohydrates are, therefore, of great significance for revolutionizing sugar chemistry to enable easier access to sugars of interest. This review begins with a brief overview of the innate reactivity of hydroxy groups of carbohydrates. It is followed by discussions about catalytic approaches to enhance, override, or be orthogonal to the innate reactivity for the transformation of carbohydrates. This review avoids making a list of chemo-and site-selective reactions, but rather focuses on summarizing the concept behind each reported transformation. The literature references were sorted into sections based on the underlying ideas of the catalytic approaches, which we hope will help readers have a better sense of the current state of chemistry and develop innovative ideas for the field.

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“…Regioselective alkylation of partially protected carbohydrates with the same stannylene acetal approach was also reported. 48…”

Section: Stannylene Acetalmentioning

confidence: 99%

Catalytic Approaches to Chemo- and Site-Selective Transformation of Carbohydrates

Yamatsugu

Kanai

2023

Chem. Rev.

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“…Various systems were reported during the last decade for the catalytic site-selective glycosylation, acylation, silylation, sulfonylation, benzylation, and carbamoylation 55 of unprotected carbohydrates. Organometallic (tin- 56 and iron-based 57-60 complexes), organoboron 61 (borinic [62][63][64] and boronic 65,66 acids), and organic 67 catalysts were involved in these transformations. Such processes found useful applications in the selective protection of sugars.…”

Section: Recent Advances In the Catalytic Site-selective Alkylation O...mentioning

confidence: 99%

“…69 In the same fashion, a simpler procedure involving dimethyltin dichloride was developed that did not require the sequential generation of a transient stannylene acetal. 56 A representative example of this protocol is given in Scheme 8. The protocol involved a stoichiometric amount of silver(I) oxide that activated the halide reactant and enabled the reaction to be carried at room temperature.…”

Section: Tin-based Catalystsmentioning

confidence: 99%

Towards better syntheses of partially methylated carbohydrates?

2022

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“…As a result, the transformation was carried out without other additive. The first attempts using iron tris(diisobutyrylmethane) (Fe-(dibm) 3 ) 19 or Me 2 SnCl 2 20 were underwhelming, as these catalysts provided complex mixtures of carbamoylated products (Table 1, entries 2 and 3), even when the reaction was performed at room temperature. As tin-and iron-based catalysts enabled a wide range of site-selective transformations of carbohydrates, these results highlighted the challenging reactivity of 1-carbamoylimidazole compared to other electrophiles.…”

mentioning

confidence: 99%

Catalytic Site-Selective Carbamoylation of Pyranosides

2021

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Carbamate-bearing carbohydrates contribute to the pharmacological properties of various natural glycosides. The catalytic site-selective carbamoylation of minimally protected pyranosides was achieved for the first time to bypass protection/deprotection sequences. 1-Carbamoylimidazoles were used as the carbamoylation reagents to circumvent the harmful and unstable phosgene and isocyanates. This borinic acid catalyzed transformation granted an expedient access to the tumor cell-binding carbamoylmannoside moiety of bleomycins and analogs in yields of 56% to 89%.

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ChemInform Abstract: Dimethyltin Dichloride Catalyzed Regioselective Alkylation of cis‐1,2‐Diols at Room Temperature.

Abstract: The title reaction is carried out with the halides (II) and (V), generally under conditions A).

Cited by 3 publications

References 1 publication

Catalytic Approaches to Chemo- and Site-Selective Transformation of Carbohydrates

Catalytic Approaches to Chemo- and Site-Selective Transformation of Carbohydrates

Towards better syntheses of partially methylated carbohydrates?

Catalytic Site-Selective Carbamoylation of Pyranosides

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