Radicals and Carbohydrates

Pérez‐Martín, Inés; Suárez, Ernesto

doi:10.1002/9781119953678.rad031

Cited by 14 publications

(16 citation statements)

References 299 publications

(285 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Radical-mediated transformations have featured prominently in the history of carbohydrate synthesis. Although a detailed discussion of the historical aspects of radical methods in carbohydrate synthesis is outside the scope of this review, past efforts have enabled a wide range of valuable transformations. , Historically, the selective generation of a desired sugar radical required prefunctionalization of the substratefurnishing the sugar with a weak bond susceptible to homolytic or mesolytic scissionand necessitated the application of stoichiometric reagents or harsh conditions. That is, challenges attendant to radical generation prevented the full realization of radical reactions to transform carbohydrate feedstocks.…”

Section: Introductionmentioning

confidence: 99%

Selective Transformations of Carbohydrates Inspired by Radical-Based Enzymatic Mechanisms

2021

View full text Add to dashboard Cite

Enzymes are a longstanding source of inspiration for synthetic reaction development. However, enzymatic reactivity and selectivity are frequently untenable in a synthetic context, as the principles that govern control in an enzymatic setting often do not translate to small molecule catalysis. Recent synthetic methods have revealed the viability of using small molecule catalysts to promote highly selective radical-mediated transformations of minimally protected sugar substrates. These transformations share conceptual similarities with radical SAM enzymes found in microbial carbohydrate biosynthesis and present opportunities for synthetic chemists to access microbial and unnatural carbohydrate building blocks without the need for protecting groups or lengthy synthetic sequences. Here, we highlight strategies through which radical reaction pathways can enable the site-, regio-, and diastereoselective transformation of minimally protected carbohydrates in both synthetic and enzymatic systems.

show abstract

Section: Introductionmentioning

confidence: 99%

Selective Transformations of Carbohydrates Inspired by Radical-Based Enzymatic Mechanisms

2021

View full text Add to dashboard Cite

show abstract

“…In previous papers, we have studied that the anomeric alkoxyl radical (i.e., II , Scheme ) β-fragmentation (ARF) of sugars initiated under oxidative or reductive conditions. We have shown that with the system (diacetoxyiodo)benzene (DIB)/I 2 , the reaction mechanism is strongly dependent on the polarity of the C2 substituent .…”

Section: Introductionmentioning

confidence: 99%

Synthetic Approaches to Phosphasugars (2-oxo-1,2-oxaphosphacyclanes) Using the Anomeric Alkoxyl Radical β-Fragmentation Reaction as the Key Step

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…For synthetic applications, Bernd Giese's group also made carbohydrate radicals available for the formation of carbon-carbon bonds under mild conditions [10]. Due to steric interactions, carbohydrates provide high stereoselectivities [11,12], and the importance of such reactions has been reviewed many times [13][14][15][16][17][18]. Furthermore, under appropriate conditions, 2-deoxy sugars can be synthesized from bromo sugars in only one step [19].…”

Section: Introductionmentioning

confidence: 99%

Addition of Heteroatom Radicals to endo-Glycals †

Linker

2020

Chemistry

View full text Add to dashboard Cite

Radical reactions have found many applications in carbohydrate chemistry, especially in the construction of carbon–carbon bonds. The formation of carbon–heteroatom bonds has been less intensively studied. This mini-review will summarize the efforts to add heteroatom radicals to unsaturated carbohydrates like endo-glycals. Starting from early examples, developed more than 50 years ago, the importance of such reactions for carbohydrate chemistry and recent applications will be discussed. After a short introduction, the mini-review is divided in sub-chapters according to the heteroatoms halogen, nitrogen, phosphorus, and sulfur. The mechanisms of radical generation by chemical or photochemical processes and the subsequent reactions of the radicals at the 1-position will be discussed. This mini-review cannot cover all aspects of heteroatom-centered radicals in carbohydrate chemistry, but should provide an overview of the various strategies and future perspectives.

show abstract

Radicals and Carbohydrates

Abstract: CO Me [Ru(bpy) 3 ](BF 4 ) 2 iPr 2 NEt, hn CO 2 Me AcO AcO AcO 21  EtO 2 C CO 2 Et Me N Me 28 H AcO 23 65 Scheme 7 Synthesis of C-ketosides by intermolecular addition of C-glycos-1-yl radicals to double bonds.

Cited by 14 publications

References 299 publications

Selective Transformations of Carbohydrates Inspired by Radical-Based Enzymatic Mechanisms

Selective Transformations of Carbohydrates Inspired by Radical-Based Enzymatic Mechanisms

Synthetic Approaches to Phosphasugars (2-oxo-1,2-oxaphosphacyclanes) Using the Anomeric Alkoxyl Radical β-Fragmentation Reaction as the Key Step

Addition of Heteroatom Radicals to endo-Glycals †

Contact Info

Product

Resources

About