<i>De novo</i>asymmetric Achmatowicz approach to oligosaccharide natural products

Kim, Sugyeom; Oiler, Jeremy; Xing, Yalan; O’Doherty, George A.

doi:10.1039/d2cc05280f

Cited by 10 publications

(7 citation statements)

References 179 publications

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“…The exploitation of the densely functionalized Achmatowicz dihydropyranones in organic synthesis has been reported in many instances. , The hemiacetal and ketone groups received particular attention as numerous oxidations of the hemiacetal − and reductions of the ketone group − have been reported. To a lesser extent, the reduction of the olefin has also been described. ,, …”

Section: Introductionmentioning

confidence: 99%

Ru-Catalyzed Isomerization of Achmatowicz Derivatives: A Sustainable Route to Biorenewables and Bioactive Lactones

et al. 2023

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A Ru-catalyzed isomerization of Achmatowicz derivatives that opens unexplored routes to diversify the biogenic furanic platform is reported. The mechanistic insights of this formally redox-neutral intramolecular process were studied computationally and by deuterium labeling. The transformation proved to be a robust synthetic tool to achieve the synthesis of bioderived-monomers and a series of 4-keto-δ-valerolactones that further enabled the development of a flexible strategy for the synthesis of acetogenins. A concise and protective group-free asymmetric total synthesis of two natural products, namely, (S,S)muricatacin and the (S,S)-L-factor, is also described.

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Section: Introductionmentioning

confidence: 99%

Ru-Catalyzed Isomerization of Achmatowicz Derivatives: A Sustainable Route to Biorenewables and Bioactive Lactones

et al. 2023

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“…12 As shown in Scheme 1c, borate esters demonstrated high reactivity and reacted with four-membered heterocyclic rings directly to form new C−O and C−C bonds without the requirement of transition-metal catalysis, 13 but their application in glycosylation was quite rare. 14 Based on the nature of borate esters, our long-term interest in glycosylation, 15 and previous Pd-catalyzed glycosylation, 16 herein, we report a novel approach to Oglycosylation using 3,4-O-carbonate glycals as the donor and borate esters as the acceptor (Scheme 1d). While 2,3unsaturated-β-O-glycosides were obtained in up to 90% yield under palladium catalysis, 2-deoxy α-O-glycosides were generated in up to 89% yield through copper catalysis at room temperature.…”

Section: ■ Introductionmentioning

confidence: 99%

Stereoselective Synthesis of O-Glycosides with Borate Acceptors

Zhao

Zhang

et al. 2023

J. Org. Chem.

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Borate esters have been applied widely as coupling partners in organic synthesis. However, the direct utilization of borate acceptors in O-glycosylation with glycal donors remains underexplored. Herein, we describe a novel O-glycosylation resulting in the formation of 2,3-unsaturated O-glycosides and 2deoxy O-glycosides mediated by palladium and copper catalysis, respectively. This O-glycosylation method tolerated a broad scope of trialkyl/triaryl borates and various glycals with exclusive stereoselectivities in high yields. All the desired aliphatic/aromatic O-glycosides and 2-deoxy O-glycosides were generated successfully, without the hemiacetal byproducts and O→C rearrangement because of the nature of borate esters. The utility of this strategy was demonstrated by functionalizing the 2,3-unsaturated glycoside products to form saturated β-O-glycosides, 2,3-deoxy O-glycosides, and 2,3-epoxy O-glycosides.

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“…Chain compounds are composed of levulinic acid [ 22 , 23 ], diols [ 24 , 25 , 26 ], polyols [ 27 , 28 , 29 ], 2,5-hexanedione [ 30 , 31 , 32 ], and 1-hydroxy-2,5-hexanedione [ 31 , 32 , 33 , 34 ], which are all valuable chemicals with a wide range of application. Ring compounds contain non-furan heterocycles [ 35 , 36 , 37 , 38 ] and carbon rings. In 2012, Hronec et al [ 39 ] first reported the conversion of furfural to cyclopentanone (CPO), and then Ohyama et al [ 40 ] realized the transformation of HMF to a cyclopentanone derivative, 3-hydroxymethylcyclopentanone (HCPN).…”

Section: Introductionmentioning

confidence: 99%

A Comprehensive Review on Metal Catalysts for the Production of Cyclopentanone Derivatives from Furfural and HMF

Duan

Cheng

et al. 2023

Molecules

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The catalytic transformation of biomass-based furan compounds (furfural and HMF) for the synthesis of organic chemicals is one of the important ways to utilize renewable biomass resources. Among the numerous high-value products, cyclopentanone derivatives are a kind of valuable compound obtained by the hydrogenation rearrangement of furfural and HMF in the aqueous phase of metal–hydrogen catalysis. Following the vast application of cyclopentanone derivatives, this reaction has attracted wide attention since its discovery, and a large number of catalytic systems have been reported to be effective in this transformation. Among them, the design and synthesis of metal catalysts are at the core of the reaction. This review briefly introduces the application of cyclopentanone derivatives, the transformation mechanism, and the pathway of biomass-based furan compounds for the synthesis of cyclopentanone derivatives. The important progress of metal catalysts in the reaction since the first report in 2012 up to now is emphasized, the characteristics and catalytic performance of different metal catalysts are introduced, and the critical role of metal catalysts in the reaction is discussed. Finally, the future development of this transformation process was prospected.

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De novoasymmetric Achmatowicz approach to oligosaccharide natural products

Abstract: The development and application of the asymmetric synthesis of oligosaccharides from achiral starting materials is reviewed. This de novo asymmetric approach centers around the use of asymmetric catalysis for the...

Cited by 10 publications

References 179 publications

Ru-Catalyzed Isomerization of Achmatowicz Derivatives: A Sustainable Route to Biorenewables and Bioactive Lactones

Ru-Catalyzed Isomerization of Achmatowicz Derivatives: A Sustainable Route to Biorenewables and Bioactive Lactones

Stereoselective Synthesis of O-Glycosides with Borate Acceptors

A Comprehensive Review on Metal Catalysts for the Production of Cyclopentanone Derivatives from Furfural and HMF

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