ChemInform Abstract: De novo Asymmetric Synthesis of the Pyranoses: From Monosaccharides to Oligosaccharides

Aljahdali, Alhanouf Z; Shi, Pei Yong; Zhong, Yashan; O’Doherty, George A.

doi:10.1002/chin.201431254

Cited by 4 publications

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“…Synthesis of l -sugars by de novo approaches has attracted much attention since Masamune, Sharpless, and co-workers (1983) prepared all eight l -hexoses through asymmetric epoxidation. , Several other approaches have been disclosed which the will be described here. , The advantages of de novo synthesis are (1) use of inexpensive and available starting materials, (2) conversion of achiral substrates into chiral products via catalyst-controlled induction, and (3) use of small quantities of the catalyst. One the other hand, the de novo approaches are not always stereoselective, lowering the yield and requiring (often tedious) purification.…”

Section: De Novo Syntheses Of L-aldohexosesmentioning

confidence: 99%

Synthesis of l-Hexoses

2015

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Section: De Novo Syntheses Of L-aldohexosesmentioning

confidence: 99%

Synthesis of l-Hexoses

2015

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“…The Achmatowicz rearrangement (AR) consists of an oxidative ring-expansion rearrangement of readily available 2-furfuryl alcohols 1 to 6-hydroxy-3-pyranones 2 (also known as pyranuloses) (Scheme ). , Due to their dense functionalization, the AR products 2 constitute useful starting materials for the preparation of an ample variety of molecules with dihydropyran or tetrahydropyran core, such as dihydropyranones, oxidopyryliums, δ-lactones, or pyranoses …”

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confidence: 99%

“…In particular, we have focused our attention on finding selective reaction conditions for the stereoselective replacement of the γC–O bond in 2 by a γC–C bond, and on stereoselective conjugate addition reactions to OH-unprotected 2 , both of them under transition-metal-free conditions (Scheme ). , Depending on the reactants and reaction conditions, these transformations will lead selectively to dihydropyranones 10 , tetrahydropyranones 12 , , or 1,4-dicarbonyl compounds 13 . In addition, we will consider the application of these findings to the one-pot synthesis of highly functionalized pyrroles ( 14 , 15 ) …”

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“…1,2 Due to their dense functionalization, the AR products 2 constitute useful starting materials for the preparation of an ample variety of molecules with dihydropyran or tetrahydropyran core, such as dihydropyranones, oxidopyryliums, δ-lactones, or pyranoses. 3 Thus, for example, AR products participate as glycosyl donors in Pd-catalyzed glycosylation reactions (2 → 3, Feringa−O'Doherty O-glycosylation), 4 in bicycloketalization reactions (2 → 4), 5 as 1,3-dipoles in [5 + 2]-cycloadditions with alkenes under basic conditions (2 → 5), 6 as 2π components in phosphine-catalyzed [3 + 2]-cycloaddition reactions with allenoates (2 → 6), 7 as 2π components in Pdcatalyzed oxa-[3 + 2]-cycloaddition reactions with 1,3dicarbonyl compounds (2 → 7), 8 or in the Kishi reduction, which leads to cis-2,6-dihydropyranones 8. 9 Additionally, by means of a two-step sequence consisting of elimination (2 → 9) followed by Heck−Matsuda arylation (Pd-catalyzed coupling with aryldiazonium salts), they may also give rise to trans-2,6-dihydropyranones 10.…”

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confidence: 99%

“…13 C NMR (75 MHz, CDCl 3 ) δ 142. 3,140.2,138.5,129.4,129.2,128.0,127.7,126.7,125.6,124.3,122.2,121.8,103.6,62.3,50.8,40.0,23.0 ppm. Anal.…”

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Selective Functionalization of Achmatowicz Rearrangement Products by Reactions with Potassium Organotrifluoroborates under Transition-Metal-Free Conditions

2018

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The repertoire of synthetic transformations of the products of the Achmatowicz rearrangement has been expanded by exploring their reactivity with potassium organotrifluoroborates in the absence of transition metals. Depending on the reaction conditions and the substitution pattern of the starting material, the reaction may lead to the stereoselective synthesis of dihydropyranones (2,6- trans), tetrahydropyranones (2,3- cis-2,6- cis) or functionalized 1,4-dicarbonyl compounds. The method has also been adapted for the one-pot synthesis of functionalized pyrroles.

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Achmatowicz Rearrangement-Inspired Development of Green Chemistry, Organic Methodology, and Total Synthesis of Natural Products

2022

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Metrics & MoreArticle Recommendations CONSPECTUS:The six-membered heterocycles containing oxygen and nitrogen (tetrahydropyrans, pyrans, piperidines) are among the most common heterocyclic structures ubiquitously present in bioactive molecules such as carbohydrates, smallmolecule drugs, and natural products. Chemical synthesis of fully functionalized pyrans and piperidines is a research theme of practical importance and scientific significance and, thus, has attracted continuous interest from synthetic chemists. Among the numerous synthetic approaches, Achmatowicz rearrangement (AchR) represents a general and unique strategy that uses biomass-derived furfuryl alcohols as the renewable starting material to obtain fully functionalized six-membered oxygen/nitrogen heterocycles, which provides golden opportunities for organic chemists to address various synthetic challenges. This Account summarizes our 10 years of work on exploiting AchR to address some challenges in organic synthesis ranging from green chemistry and organic methodology to the total synthesis of natural products. We enabled the sustainable and safe use of AchR in a small (academia) or large (industrial) scale by developing two generations of green approaches for AchR (oxone-halide and Fenton-halide), which largely eliminate the use of the most popular, but more toxic and expansive, NBS and m-CPBA. This triggered our intensive interest in developing new green chemistry for important organic reactions, in particular, halogenation/oxidation reactions involving reactive halogenating species with the aim of eliminating the use of commonly used toxic halogen agents such as elemental bromine, chlorine gas, and various N-haloamide reagents (NBS, NCS, and NIS). We successfully employed oxone-halide and Fenton-halide as green alternatives to several mechanistically related organic reactions including arene/alkene halogenation, oxidation or oxidative rearrangement of indoles, oxidation of alcohols/thioacetals, and oxidative halogenation of aldoximes for the in situ generation of nitrile oxide. These green reactions are expected to have a solid impact on the future of organic synthesis in academia and industries. We expanded the synthetic utility of AchR by exploring several new transformations of AchR products and developed a cascade reductive ring expansion, reductive deoxygenation/Heck−Matsuda arylation, palladium-catalyzed C-arylation, and regiodivergent [3 + 2] cycloaddition with 1,3-dicarbonyls. These methodologies offer a new avenue to fully functionalized six-membered heterocycles.The synthetic utility of AchR was demonstrated in our total synthesis of 28 natural products with a pyran/piperidine moiety. The AchR-based strategy endows the total synthesis with scalability, sustainability, and flexibility. The green and scalable approaches developed in our lab for AchR allow us to easily obtain decagrams of synthetically valuable pyrans and/or piperidines with low risk and low cost from biomass-derived furfuryl alcohol/aldehyde.

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ChemInform Abstract: De novo Asymmetric Synthesis of the Pyranoses: From Monosaccharides to Oligosaccharides

Cited by 4 publications

References 1 publication

Synthesis of l-Hexoses

Synthesis of l-Hexoses

Selective Functionalization of Achmatowicz Rearrangement Products by Reactions with Potassium Organotrifluoroborates under Transition-Metal-Free Conditions

Achmatowicz Rearrangement-Inspired Development of Green Chemistry, Organic Methodology, and Total Synthesis of Natural Products

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