Catalytic activation of glycosyl phosphates for stereoselective coupling reactions

Levi, Samuel M.; Li, Qiuhan; Rötheli, Andreas R.; Jacobsen, Eric N.

doi:10.1073/pnas.1811186116

Cited by 65 publications

(43 citation statements)

References 32 publications

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“…On the organocatalytic front [60][61][62][63][64] , seminal studies by Galan and McGarrigle et al demonstrated the utility of thiourea catalysis in accessing 2-deoxyglycosides via mild organocatalytic conditions 47,56 . However, significant limitations still exist in such protocols.…”

mentioning

confidence: 99%

A robust and tunable halogen bond organocatalyzed 2-deoxyglycosylation involving quantum tunneling

Xu¹,

Rao²,

Weigen³

et al. 2020

Nat Commun

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The development of noncovalent halogen bonding (XB) catalysis is rapidly gaining traction, as isolated reports documented better performance than the well-established hydrogen bonding thiourea catalysis. However, convincing cases allowing XB activation to be competitive in challenging bond formations are lacking. Herein, we report a robust XB catalyzed 2-deoxyglycosylation, featuring a biomimetic reaction network indicative of dynamic XB activation. Benchmarking studies uncovered an improved substrate tolerance compared to thiourea-catalyzed protocols. Kinetic investigations reveal an autoinductive sigmoidal kinetic profile, supporting an in situ amplification of a XB dependent active catalytic species. Kinetic isotopic effect measurements further support quantum tunneling in the rate determining step. Furthermore, we demonstrate XB catalysis tunability via a halogen swapping strategy, facilitating 2-deoxyribosylations of D-ribals. This protocol showcases the clear emergence of XB catalysis as a versatile activation mode in noncovalent organocatalysis, and as an important addition to the catalytic toolbox of chemical glycosylations.

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mentioning

confidence: 99%

A robust and tunable halogen bond organocatalyzed 2-deoxyglycosylation involving quantum tunneling

Xu¹,

Rao²,

Weigen³

et al. 2020

Nat Commun

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“…Computational studies suggested the coordination of the thiourea moieties to the chloride ion activates the donor, and the amide group on 21 concomitantly enhances the nucleophilicity of the acceptor in the transition state. Glycosylations of glycosyl phosphate, using a similar bis‐thiourea catalyst, have also been reported …”

Section: Organocatalysismentioning

confidence: 90%

Recent Developments in Stereoselective Chemical Glycosylation

Ling

Bennett

2019

Asian J Org Chem

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Because of their pivotal biological functions, attention to sugars and glycobiology has grown rapidly in recent decades, leading to increased demand for homogeneous oligosaccharides. The stereoselective preparation of oligosaccharides by chemical means remains challenging and continues to be a vivid research area for organic chemists. In the past decade, new approaches and reinvestigated tradi-tional methods have transformed the field. These developments include novel catalyses, various types of glycosylation modulators and the use of photochemical energy to facilitate glycosylation. This Minireview presents a brief overview of the latest trends in chemical glycosylation, with emphasis on the stereoselective synthetic protocols developed in the past decade.[a] Dr.

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“…[18] Jacobsen explained the electronic and steric influence of the Ar groups,the kinetics and solvent effects and the mechanistic insights obtained from different transformations. [19] Theg ained mechanistic understanding allowed the Jacobsen group to tackle challenging transformations like site-selective glycosidations [20] and to exploit the cooperative reactivity of H-bond donors and Lewis acids. [21] Tuesday 7thofM ay On Tuesday morning Jonathan Clayden (University of Bristol) gave an inspiring lecture about the biomimetic function from folded molecules.W eg ained deep insight in conformational challenges.H ed escribed how the conformational understanding can lead to the design and synthesis of molecular communication devices [22] with the capability to transfer information to remote reactive sites.Heenlightened the importance of foldamers [23] (conformationally defined molecules) ( Figure 4) towards their potential ability to mimic biological function.…”

Section: Sunday 5tho Fmaymentioning

confidence: 99%