Recent Advances in Natural Products Synthesis Using Bifunctional Organocatalysts Bearing a Hydrogen‐Bonding Donor Moiety

Odagi, Minami; Nagasawa, Kazuo

doi:10.1002/ajoc.201900459

Cited by 20 publications

(14 citation statements)

References 71 publications

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“…N oncovalent catalysis constitutes one of the major pillars of organocatalysis [1][2][3][4] , by capitalizing intermolecular interactions, such as hydrogen bonds (HB) to activate specific functional groups under mild conditions. Indisputably, HB catalysis 5,6 dominates the majority of noncovalent organocatalyzed protocols, which is largely spearheaded by thiourea catalysis [7][8][9][10][11][12][13][14] . Furthermore, thiourea organocatalysis is widely dubbed as biomimetic 2 , as it derives inspiration from how enzymes capitalize noncovalent interactions to catalyze biochemical reactions [1][2][3][4] .…”

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confidence: 99%

“…Furthermore, thiourea organocatalysis is widely dubbed as biomimetic 2 , as it derives inspiration from how enzymes capitalize noncovalent interactions to catalyze biochemical reactions [1][2][3][4] . Hence, biomimetic thiourea catalysis is well recognized as a powerful synthetic tool spanning from asymmetric catalysis to natural product synthesis [5][6][7][8][9][10][11][12][13][14] .…”

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confidence: 99%

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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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confidence: 99%

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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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“…Jacobsen, [65] Takemoto, [66] Soós, [67] Connon, [68] and Rawal [69] were among the first to introduce the thiourea, urea, and squaramide moieties, which are more effective in hydrogen‐bonding than a simple hydroxy group, to a variety of chiral backbones, including the cinchona alkaloids, to obtain a plethora of highly effective and stereoselective organocatalysts. In this section, we will discuss the application of these bifunctional organocatalysts in the total synthesis of natural products [13] …”

Section: Applications In Natural Product Synthesismentioning

confidence: 99%

“…N-Heterocyclic carbenes (NHC) have found a lot of applications as excellent organocatalyst in organocatalysis due to their unique activation mode and the new reactivities they introduced. [13] In addition, besides aldehydes and ketones, Nheterocyclic carbene catalysts can also activate unactivated esters, which cannot be activated by the amine catalysts. [25] In this section, we will discuss the application these catalysts in the total synthesis of natural products.…”

Section: N-heterocyclic Carbene Catalystsmentioning

confidence: 99%

“…This fast developing field has been constantly reviewed and several review articles have appeared recently to cover the applications of specific types of organocatalysts in the total synthesis of natural products or the total synthesis of specific classes of natural products using organocatalysts [9–20] . Nonetheless, an overview of these developments is still lacking.…”

Section: Introductionmentioning

confidence: 99%

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Recent Applications of Asymmetric Organocatalytic Methods in Total Synthesis

2021

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Natural products are the great sources of drugs and leading compounds in drug discovery, as it has been estimated that most of the current medicines are derived from natural products. Total synthesis of natural products, especially those of biological activities, has been an important part of organic chemistry, which, besides its potential practical utilities, also provides new inspirations and novel synthetic methodologies. Over the past two decades, organocatalysis has been shown to be very effective in controlling the stereochemistry of the reaction products and has found many applications in the asymmetric synthesis of natural products and related compounds. In this review we will attempt to summarize some applications of asymmetric organocatalysis in the total synthesis of natural products and related compounds in the past seven years.

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Cinchona Derivatives as Bifunctional H‐bonding Organocatalysts in Asymmetric Vinylogous Conjugate Addition Reactions

Joshi

Singh

2022

Asian J Org Chem

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Asymmetric vinylogous conjugate addition reactions constitute an essential class of enantioselective CÀ C bond-forming transformations characterized by remote functionalization of substrates and the construction of distal stereocenters. After the renaissance of organocatalysis in 2000, vinylogous addition methodologies have seen new horizons of development. Cinchona alkaloids and some of their derivatives have appeared as efficient chiral catalysts in several organic transformations. Their non-toxicity, low cost, availability in pseudo-enantiomeric forms, and "open flask" reaction procedures have been the main reasons behind their success in asymmetric synthesis. These organocatalysts have also shown remarkable applications in vinylogous chemistry. This mini-review covers the developments of asymmetric vinylogous conjugate addition (VCA) reactions under bifunctional cinchona alkaloids/derivatives catalysis.

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Recent Advances in Natural Products Synthesis Using Bifunctional Organocatalysts Bearing a Hydrogen‐Bonding Donor Moiety

Cited by 20 publications

References 71 publications

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

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

Recent Applications of Asymmetric Organocatalytic Methods in Total Synthesis

Cinchona Derivatives as Bifunctional H‐bonding Organocatalysts in Asymmetric Vinylogous Conjugate Addition Reactions

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