Catalytic Activation of <i>Cis</i>-Vicinal Diols by Boronic Acids: Site-Selective Acylation of Carbohydrates

Shimada, Naoyuki; Nakamura, Yuki; Ochiai, Takayuki; Makino, Kazuishi

doi:10.1021/acs.orglett.9b01231

Cited by 35 publications

(28 citation statements)

References 64 publications

(26 reference statements)

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“…[8][9][10] They are important building blocks in the fields of bioactive compounds (Figure 2) [14][15][16][17] and material sciences. [18,19] They have also found applications, as catalysts, [20][21][22] protecting group of diols, [23] molecular recognition sensors, [24] separation tools, [25] and cell-penetrating carriers for peptide delivery. [26,27]…”

Section: Reactivity and Importance Of Alkenylboronates And Arylboronatesmentioning

confidence: 99%

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

et al. 2021

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Organoboron compounds, especially alkenylboronates and arylboronates are highly useful reagents and versatile building blocks in the modern synthetic chemistry toolbox. This review focuses on copper-catalyzed routes to access alkenyl-and arylboronate esters. Various copper salts and ligands have been employed to access them in excellent regio-and stereoselectivity as well as high yields. Both addition and substitution reactions to alkenylboronates have been highlighted based on various methodologies including hydroboration, carboboration, borylative opening of propargyl three-and four-membered rings, dehalogenative borylation of alkenyl bromides and iodides, defluoroborylation of fluoroalkenes and direct C(sp 2 )À H bond activation of alkenes. Preparation of arylboronates involving borylation of aryl halides, C(sp 2 )À H borylation of arenes and cascade 1,3-halogen migration/borylation of 2halostyrenes have been reviewed. Mechanistic aspects of those borylation reactions are discussed briefly.

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Section: Reactivity and Importance Of Alkenylboronates And Arylboronatesmentioning

confidence: 99%

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

et al. 2021

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“…With the required starting material in hand, we turned our attention to the screening of initially described ethanolamine ester of diphenylborinic acid catalyst (Taylor's catalyst) 48 along with a boronic acid catalyst recently developed by Shimada and coworkers. 49 Under classic conditions, both catalysts afforded conversion to the desired product (Scheme 2). Encouraged by this finding, we therefore optimized the reaction with the Shimada catalyst since it offered slightly higher catalytic activity in these initial experiments.…”

Section: Scheme 1: Preparation Of the Catalysis-precursor Bisallyl-op1118mentioning

confidence: 99%

Novel Fidaxomicin Antibiotics through Site-Selective Catalysis

Dailler¹,

Dorst²,

Schäfle³

et al. 2020

Preprint

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<div><div><div><p>Fidaxomicin (FDX) is a marketed antibiotic for the treatment Clostridium difficile infections (CDI). Although showing interesting antibacterial properties against many Gram-positive bacteria, the application of this antibiotic is currently limited to treatment of CDI. Semisynthetic modifications present a promising strategy to improve its pharmacokinetic properties and also circumvent resistance development by broadening the structural diversity of derivatives. Based on a rational design using a cryo-EM structure analysis, we implemented two strategic site- selective catalytic reactions with a special emphasis to study the role of the carbohydrate units. Site-selective introduction of various ester moieties on the noviose as well as a Tsuji-Trost type rhamnose cleavage allowed the synthesis of novel fidaxomicin analogs with promising antibacterial activities against C. difficile and M. tuberculosis.</p></div></div></div>

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“…In fact, there are reports in which site-selective acylation has been considered a powerful means for synthesizing partially acylated polyol natural products with focus on structure-activity relationships. [20][21][22][23][24][25] In this regard, we have recently reported that imidazole-containing boronic acid acts as a highly active catalyst for the site-selective acylation of carbohydrates 26) (Chart 1). Our catalytic reaction allows us to introduce a wide variety of acyl functional moieties in the equatorial position of cis-vicinal diol of carbohydrates in a highly selective manner.…”

Section: Introductionmentioning

confidence: 99%

Boronic Acid-Catalyzed Final-Stage Site-Selective Acylation for the Total Syntheses of <i>O</i>-3′-Acyl Bisabolol β-D-Fucopyranoside Natural Products and Their Analogues

Nakamura

Ochiai

Makino

et al. 2021

CHEMICAL & PHARMACEUTICAL BULLETIN

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The first concise total syntheses of O-3′-senecioyl α-bisabolol β-D-fucopyranoside (4a) and O-3′isovaleroyl α-bisabolol β-D-fucopyranoside (4b) were achieved through final-stage site-selective acylation via the activation of cis-vicinal diols by imidazole-containing boronic acid catalysts as a key step. This synthetic method was also effective for the syntheses of unnatural analogues with modified acyl side chains or carbohydrate moiety.

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Catalytic Activation of Cis-Vicinal Diols by Boronic Acids: Site-Selective Acylation of Carbohydrates

Cited by 35 publications

References 64 publications

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

Copper‐Catalyzed Preparation of Alkenylboronates and Arylboronates

Novel Fidaxomicin Antibiotics through Site-Selective Catalysis

Boronic Acid-Catalyzed Final-Stage Site-Selective Acylation for the Total Syntheses of <i>O</i>-3′-Acyl Bisabolol β-D-Fucopyranoside Natural Products and Their Analogues

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