Base‐Free Palladium‐Catalyzed Borylation of Aryl Chlorides with Diborons

Yamamoto, Yoshimi; Matsubara, Hiroshi; Yorimitsu, Hideki; Osuka, Atsuhiro

doi:10.1002/cctc.201600456

Cited by 32 publications

(23 citation statements)

References 95 publications

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“…The aryl chloride borylation is always challenging, and there were no methods available for this transformation until 2001. The first example was reported by Ishiyama et al using Pd as a catalyst and subsequently scope was expanded by others using mainly Pd and few Ni catalyst systems. − In 2014, Bedford et al reported iron catalyzed borylation of alkyl, allyl and aryl halides, but only chlorobenzene could be borylated in a poor yield of 5% . Metal-free photoinduced C–X and dual C–H/C–X borylation of haloarenes were reported by Larionov et al, and pyridine-catalyzed radical borylation of aryl halides was reported by Jiao et al, but only two aryl chlorides have been described in each case.…”

Section: Introductionmentioning

confidence: 99%

Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides

2018

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An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields. A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselectivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle may rely on a cobalt(I)–(III) redox couple.

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Section: Introductionmentioning

confidence: 99%

Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides

2018

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“…[ 10a,13 ] At first, the boronic ester‐functionalized IM unit is prepared by a facile synthesis (Figure S1a, Supporting Information). [ 14 ] This functionalization allows IM to participate in any Suzuki cross‐coupling reactions, thus being expandable to produce many different types of CPs. [ 15 ] It is confirmed that boronic ester functional groups are not affected during the imine reaction, evidenced by nuclear magnetic resonance (NMR) and mass spectroscopy (Figure S2, Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

Disintegrable n‐Type Electroactive Terpolymers for High‐Performance, Transient Organic Electronics

Park

Kim

et al. 2021

Adv Funct Materials

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Degradable organic semiconductors have significant potential for transient and biomedical organic electronics, but there have been only a few studies on fully degradable conjugated polymers (CPs) that achieve high electrical performance. In addition, these examples are limited to p‐type CPs. In this study, a series of fully degradable n‐type CPs, naphthalene diimide (NDI)‐based terpolymer (PNDIT2/IM‐f) are developed. The incorporation of an imine linker (IM) into the CP backbone affords the capability of facile hydrolysis degradation while maintaining efficient π‐conjugations and excellent electrical properties. An additional benefit of this molecular design is the systematic tunability of the degradation characteristics and electrical performance depending on the IM content (fIM). At the optimal point (fIM = 0.45) that enables complete degradation of the polymer under acidic conditions, the resulting PNDIT2/IM‐0.45 film exhibits high electron mobility (μe) of 0.04 cm2 V−1 s−1 in organic field‐effect transistors (OFETs), demonstrating excellent potential as transient OFETs. The high μe value is mainly attributed to the enlarged edge‐on orientations and tighter stacking of PNDIT2/IM‐f crystallites as increasing fIM. Thus, this study provides useful guidelines for the design of fully degradable n‐type CPs and establishes an important correlation between the molecular structure−electronic performance−transient properties.

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“…The base was selected as a key parameter as its role in these reactions has not been comprehensively explored and is not mechanistically understood. Although base-free versions of the borylation have been reported, 6 a carboxylate salt seems crucial for the reactivity of this system. A systematic base screen was performed using 4bromobenzonitrile as model substrate (eq 1).…”

Section: ■ Introductionmentioning

confidence: 99%

Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study

et al. 2020

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Aryl boronic acids and esters are important building blocks in API synthesis. The palladium-catalyzed Suzuki-Miyaura borylation is the most common method for their preparation. This paper describes an improvement of the current reaction conditions. By using lipophilic bases such as potassium 2-ethyl hexanoate, the borylation reaction could be achieved at 35 °C in less than 2 h with very low palladium loading (0.5 mol %). A preliminary mechanistic study shows a hitherto unrecognized inhibitory effect by the carboxylate anion on the catalytic cycle, whereas 2-ethyl hexanoate minimizes this inhibitory effect. This improved methodology enables borylation of a wide range of substrates under mild conditions.

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Base‐Free Palladium‐Catalyzed Borylation of Aryl Chlorides with Diborons

Cited by 32 publications

References 95 publications

Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides

Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides

Disintegrable n‐Type Electroactive Terpolymers for High‐Performance, Transient Organic Electronics

Improvement in the Palladium-Catalyzed Miyaura Borylation Reaction by Optimization of the Base: Scope and Mechanistic Study

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