Reversing the Stereoselectivity of a Palladium‐Catalyzed O‐Glycosylation through an Inner‐Sphere or Outer‐Sphere Pathway

Xiang, Shao‐Hua; Hoang, Kim Le Mai; He, Jingxi; Tan, Yu; Liu, Xuewei

doi:10.1002/anie.201408739

Cited by 52 publications

(29 citation statements)

References 46 publications

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“…Previously, the application of this technique to glycosidic bond formation has been hampered by the difficulty in the formation of the palladium π-allyl intermediates and their poor reactivity in the electron-rich glycal systems [ 120 ]. To overcome this challenge the Liu group explored the application of palladium π-allyl intermediates to O -glycosylation through the use of a picoloyl group to direct palladium binding at the C-3 position [ 121 ]. Glycosylation results are indicative of two reaction pathways with differing in the selectivity outcome based on the hard/soft properties of the nucleophiles.…”

Section: Reviewmentioning

confidence: 99%

Intramolecular glycosylation

Jia¹,

Demchenko²

2017

Beilstein J. Org. Chem.

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Carbohydrate oligomers remain challenging targets for chemists due to the requirement for elaborate protecting and leaving group manipulations, functionalization, tedious purification, and sophisticated characterization. Achieving high stereocontrol in glycosylation reactions is arguably the major hurdle that chemists experience. This review article overviews methods for intramolecular glycosylation reactions wherein the facial stereoselectivity is achieved by tethering of the glycosyl donor and acceptor counterparts.

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Section: Reviewmentioning

confidence: 99%

Intramolecular glycosylation

Jia¹,

Demchenko²

2017

Beilstein J. Org. Chem.

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“…However, the polyols that can be effectively targeted in such reaction sequences are limited because most polyols are not sufficiently soluble in organic solvents. This problem is of central importance in carbohydrate chemistry, where solubility and regioselectivity is the major obstacle to the preparation of advanced compounds from readily available saccharide derivatives . Furthermore, these catalyst driven reactions also possess troublesome shortcomings including their inherent toxicity and the high cost of catalysts and the necessity to pre‐protect secondary hydroxyl groups.…”

Section: Introductionmentioning

confidence: 99%

Catalyst Free Selective Monobenzoylation of Diols with Benzoyl Cyanide: A Robust and Regioselective Strategy

et al. 2018

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A general and robust strategy for regio‐ and chemoselective benzoylation of diols and polyols was developed under catalyst‐free reaction conditions. This approach is highly flexible in generating a diverse range of 1,2‐, 1,3‐, and 1,4‐monobenzoylated‐adducts in excellent yields without the involvement of expensive catalysts. Collectively, these results have implications in reducing the burden of cost and toxicity associated with the catalysts used in earlier methods.

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“…287 Accordingly, a variety of O -glycosidation methods, 288, 289 using the Pd-catalyzed Tsuji-Trost allylic alkylation were developed to link monosaccharides. 290-294 These methods involved the work of Lee, 295, 296 Feringa, 146 O'Doherty, 81, 145 Liu, 297-299 and Rhee. 300 …”

Section: Introductionmentioning

confidence: 99%

“…302 Mezzettiaside-2 ( 271 ) and congeners were synthesized as anticancer/antibiotic oligosaccharides. 88 Merremoside D 272 299 and carbohydrates including digitoxin ( 273 , anticancer properties), 303 vineomycinone B2 ( 274 ), 304 vineomycin B2 trisaccharide ( 276 ) 305 (antitumor and antibacterial activities), methymycin analogues such as 275 (antibiotic activity), 306 and landomycins A and E ( 277a,b , antitumor activity) 307 were also synthesized using these protocols.…”

Section: Introductionmentioning

confidence: 99%

Achmatowicz reaction and its application in the syntheses of bioactive molecules

Ghosh

Brindisi

2016

RSC Adv.

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Substituted pyranones and tetrahydropyrans are structural subunits of many bioactive natural products. Considerable efforts are devoted toward the chemical synthesis of these natural products due to their therapeutic potential as well as low natural abundance. These embedded pyranones and tetrahydropyran structural motifs have been the subject of synthetic interest over the years. While there are methods available for the syntheses of these subunits, there are issues related to regio and stereochemical outcomes, as well as versatility and compatibility of reaction conditions and functional group tolerance. The Achmatowicz reaction, an oxidative ring enlargement of furyl alcohol, was developed in the 1970s. The reaction provides a unique entry to a variety of pyranone derivatives from functionalized furanyl alcohols. These pyranones provide convenient access to substituted tetrahydropyran derivatives. This review outlines general approaches to the synthesis of tetrahydropyrans, covering general mechanistic aspects of the Achmatowicz reaction or rearrangement with an overview of the reagents utilized for the Achmatowicz reaction. The review then focuses on the synthesis of functionalized tetrahydropyrans and pyranones and their applications in the synthesis of natural products and medicinal agents.

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Reversing the Stereoselectivity of a Palladium‐Catalyzed O‐Glycosylation through an Inner‐Sphere or Outer‐Sphere Pathway

Cited by 52 publications

References 46 publications

Intramolecular glycosylation

Intramolecular glycosylation

Catalyst Free Selective Monobenzoylation of Diols with Benzoyl Cyanide: A Robust and Regioselective Strategy

Achmatowicz reaction and its application in the syntheses of bioactive molecules

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