Bedford-Type Palladacycle-Catalyzed Miyaura Borylation of Aryl Halides with Tetrahydroxydiboron in Water

Zernickel, Anna; Du, Weiyuan; Ghorpade, Seema; Sawant, Dinesh N.; Makki, Arwa A.; Sekar, Nagaiyan; Eppinger, Jörg

doi:10.1021/acs.joc.7b02771

Cited by 16 publications

(13 citation statements)

References 98 publications

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“…The 4-fluoro substrate ( 2f ) was obtained without any dehalogenated product. The borylation of bromophenol ( 1g ) resulted in a high yield (97%), which is higher than that afforded by previous transition-metal-catalyzed (Pd and Ni) borylation methods. Nitrile ( 1h ) was not reduced under the reaction conditions.…”

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confidence: 74%

“…Using BBA, aryl chloride was converted to boronic acid directly without any deprotection step. Following this research, BBA has been used as a diboron source in the transition-metal-catalyzed borylation of aryl halides. − BBA has also been used in photoinduced transition-metal-free borylation reactions (Scheme b). , Under optimized conditions, aryl halides are converted to boronic acid in the presence of hv and BBA. However, the photoinduced reaction requires a quartz reactor and strong light sources.…”

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confidence: 99%

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Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source

2020

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In this study, we developed a simple transition-metal-free borylation reaction of aryl bromides. Bis-boronic acid (BBA), was used, and the borylation reaction was performed using a simple procedure at a mild temperature. Under mild conditions, aryl bromides were converted to arylboronic acids directly without any deprotection steps and purified by conversion to trifluoroborate salts. The functional group tolerance was considerably high. The mechanism study suggested that this borylation reaction proceeds via a radical pathway.

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confidence: 74%

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confidence: 99%

Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source

2020

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“…2‐(2,4‐Dimethylphenyl)‐4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolane (8b) : Orange oil. Yield: 362 mg (78 %).…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Amino‐ and Hydroxymethyl Benzoxaboroles: Prominent Scaffolds for Further Functionalization

et al. 2019

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Herein, we describe the development of a short, simple, and efficient synthesis of amino‐ and hydroxymethyl‐substituted benzoxaboroles. The key step in our strategy was the early stage incorporation of the boron by the borylation of an aniline. The formed boronates were then elaborated to the final products in two additional steps, usually in good yields. The synthetic sequence was amenable to be performed on a preparative scale and 4‐amino benzoxaborole 4b and 6‐hydroxymethyl benzoxaborole 10c have been prepared, without any significant decrease in the overall yield. The amino and hydroxymethyl present at the molecules are useful for further elaboration and/or conjugation to bioactive molecules and therefore we believe that this method should be useful in the development of new compounds for Medicinal Chemistry.

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“…TDB is a frequently used borylation reagent that has rarely been used in the literature for reduction reactions. 19,20 The LTMNPs used for catalysis are stabilized here by graphene quantum dots (GQDs), and for this purpose, a new and green method of synthesis of GQDs is established from commercial glucan.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Experiments using D 2 O instead of water including kinetic isotope effect (KIE) allow confirming and precising the mechanism. TDB is a frequently used borylation reagent that has rarely been used in the literature for reduction reactions. , The LTMNPs used for catalysis are stabilized here by graphene quantum dots (GQDs), and for this purpose, a new and green method of synthesis of GQDs is established from commercial glucan. GQDs can be regarded as small pieces of graphene (less than 100 nm), and they are gaining extensive attraction because of excellent hydrophilicity, low biotoxicity, and stable photoluminescent (PL) properties .…”

Section: Introductionmentioning

confidence: 99%

Catalyzed Hydrolysis of Tetrahydroxydiboron by Graphene Quantum Dot-Stabilized Transition-Metal Nanoparticles for Hydrogen Evolution

Chen

Shen

Huang

et al. 2020

ACS Sustainable Chem. Eng.

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The search of new H2 evolution systems avoiding fossil sources and their mechanisms is a priority in the 21st century society. Hydrolysis of tetrahydroxydiboron (TDB), a current borylation source in the literature, is used here for H2 evolution for the first time. It is catalyzed by graphene quantum dot-stabilized nanoparticles (NPs). With RhNP- or PtNP-catalyzed reactions, D2 formation from D2O confirms that water is the only hydrogen source. Kinetic isotopic effects yield k H/k D = 5.91 and 4.18, strongly suggesting double water O–H bond cleavage on the NP surface in the rate-limiting step. The most efficient catalysts are the RhNP and PtNP (total turnover frequencies: 3658 and 4603 molH2 ·molcat –1·min–1, respectively). The order of catalytic activity is as follows: PtNP > RhNP > AuNP > PdNP > IrNP > RuNP, and a catalytic mechanism of TDB hydrolysis is proposed.

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Bedford-Type Palladacycle-Catalyzed Miyaura Borylation of Aryl Halides with Tetrahydroxydiboron in Water

Cited by 16 publications

References 98 publications

Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source

Transition-Metal-Free Borylation of Aryl Bromide Using a Simple Diboron Source

Synthesis of Amino‐ and Hydroxymethyl Benzoxaboroles: Prominent Scaffolds for Further Functionalization

Catalyzed Hydrolysis of Tetrahydroxydiboron by Graphene Quantum Dot-Stabilized Transition-Metal Nanoparticles for Hydrogen Evolution

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