Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters

Ishiyama, Tatsuo; Murata, Miki; Miyaura, Norio

doi:10.1021/jo00128a024

Cited by 1,506 publications

(980 citation statements)

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“…In 1995, Miyaura and co-workers reported the synthesis of arylboronates by the Pd catalyzed cross-coupling of tetraalkoxydiboron reagents with haloarenes, including 3-iodobenzothiophene. 23 Subsequently, Masuda and co-workers devised related conversions using dialkoxyboranes, 24 including the synthesis of 2-thienyl boronate esters. 25 These transformations were important advances because (i) substoichiometric quantities of Pd catalysts served as the metalating agents, and (ii) the mild reaction conditions can accommodate functional groups that are incompatible with organomagnesium or organolithium reagents.…”

Section: Resultsmentioning

confidence: 99%

Iridium-catalyzed borylation of thiophenes: versatile, synthetic elaboration founded on selective C–H functionalization

et al. 2008

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Iridium-catalyzed borylation has been applied to various substituted thiophenes to synthesize polyfunctionalized thiophenes in good to excellent yields. Apart from common functionalities compatible with iridium-catalyzed borylations, additional functional group tolerance to acyl (COMe), and trimethylsilyl (TMS) groups was also observed. High regioselectivities were observed in borylation of 3-and 2,5-di-substituted thiophenes. Electrophilic aromatic C-H/C-Si bromination on thiophene boronate esters is shown to take place without breaking the C-B bond, and one-pot C-H borylation/Suzuki-Miyaura cross-coupling has been accomplished on 2-and 3-borylated thiophenes.

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Section: Resultsmentioning

confidence: 99%

Iridium-catalyzed borylation of thiophenes: versatile, synthetic elaboration founded on selective C–H functionalization

et al. 2008

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“…For the present work we made two modifications. Firstly we used aryl iodides, which generally show greater reactivity in Pd-catalyzed couplings; and secondly we used organoboron methodology based on the recently commercialized ''B-B'' reagent bis(pinacolato)diboron (27). Starting from 5-iodo-m-xylene 2, benzylic bromination followed by Gabriel synthesis gave bis-phthalimide 4.…”

Section: Resultsmentioning

confidence: 99%

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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We have previously shown that macrotricyclic host 1a is a powerful receptor for glucopyranosyl units in the nonpolar medium of chloroform. However, the solubility properties of 1a did not permit studies of the extraction of carbohydrates from aqueous solution. This paper describes the synthesis of the new variant 1b, furnished with a highly lipophilic exterior array of 12 benzyloxy substituents. In homogeneous solution, 1b behaves much as 1a, binding n-octyl ␤-D-glucoside with Ka ‫؍‬ 720 M ؊1 in CD3OH͞CDCl3 (8:92). In twophase experiments, the improved solubility of 1b allows carbohydrate extraction to be observed. Three hexoses (glucose, galactose, and mannose), two pentoses (ribose and xylose), and the two methyl glucosides are all extracted substantially into chloroform from 1 M aqueous solutions. Among the hexoses, 1b shows notable affinity and selectivity for glucose, extracting detectable amounts even from 0.1 M aqueous solutions. C arbohydrate recognition is an active area of supramolecular chemistry, motivated by the biological importance of saccharides and also by the unusual challenge represented by these complex substrates (1-13). On the one hand, carbohydrates must be recognized and processed during metabolism, whereas saccharide motifs are known to mediate cell-cell recognition, the infection of cells by pathogens, and many aspects of the immune response (14-17). On the other, carbohydrates possess structures that are fairly large, irregular, and multivalent, while being quite similar to clusters of water molecules. Even in nonpolar solvents, selective carbohydrate receptors require extended, sophisticated architectures (1, 3-6). In the presence of liquid water, the problem becomes yet more difficult. Recognition by means of boronate formation has been relatively successful (2, 7-10), but there are few effective systems for binding saccharides from water by using noncovalent bonds (1, 11-13).A receptor can be shown to discriminate between saccharide and water in one of two ways. Firstly (and most obviously), it can be studied in homogeneous aqueous solution. Secondly, it can be designed for solubility in nonpolar media and studied in a two-phase system, demonstrating the ability to extract or transport the carbohydrate (18)(19)(20)(21)(22)(23)(24). This latter approach is directly relevant to the transport of carbohydrates across biological membranes. Boron-based systems have again proved quite effective (22-24). However, for those receptors operating through noncovalent interactions, success has been limited thus far. Positive results have been obtained with the less hydrophilic saccharides at high aqueous concentrations (18, 20), but not in general with the more hydrophilic substrates such as glucose. § Recently we described the tricyclic tetraester 1a (Fig. 1), a novel receptor that showed an exceptional affinity for n-octyl ␤-D-glucoside, remarkable ␤ vs. ␣ selectivity, and the unusual ability to dissolve solid glucose in CHCl 3 (25). Although we hoped to demonstrate the extraction of glucose ...

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“…In fact, the reaction of aryl halide 2r under typical palladium-catalyzed borylation conditions [50] resulted in the decomposition of the substrate, whereas our boryl substitution method afforded the desired product 3r in 90% yield. As for the reaction mechanism, we first investigated the possibility of aryl radical mediated mechanism.…”

Section: Pmentioning

confidence: 94%

Formal Nucleophilic Boryl Substitution of Organic Halides with Silylborane/Alkoxy Base System

et al. 2014

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Boryl substitution of organohalides with a silylborane and alkoxy bases is described. This reaction can be applied to various functionalized aryl halides. Alkyl and alkenyl halides, and even sterically congested aryl bromides also provided the corresponding borylated products in high yields.Mechanistic studies indicated that neither trace transition-metal impurities nor aryl radical species involved in this reaction. (57 words)

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Palladium(0)-Catalyzed Cross-Coupling Reaction of Alkoxydiboron with Haloarenes: A Direct Procedure for Arylboronic Esters

Cited by 1,506 publications

References 0 publications

Iridium-catalyzed borylation of thiophenes: versatile, synthetic elaboration founded on selective C–H functionalization

Iridium-catalyzed borylation of thiophenes: versatile, synthetic elaboration founded on selective C–H functionalization

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Formal Nucleophilic Boryl Substitution of Organic Halides with Silylborane/Alkoxy Base System

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