Neopentylglycolborylation of Aryl Chlorides Catalyzed by the Mixed Ligand System NiCl<sub>2</sub>(dppp)/dppf

Moldoveanu, Costel; Wilson, Daniela A.; Wilson, Christopher J.; Corcoran, Patrick; Rosen, Brad M.; Percéc, Virgil

doi:10.1021/ol902155e

Cited by 71 publications

(46 citation statements)

References 29 publications

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“…Our new catalytic system has the advantage of a readily prepared catalyst requiring no additional ligands. NaOAc as our additive is mild, inexpensive, nontoxic, and easier to use compared with DIPEA and Et 3 N employed by the groups of Percec, Murata and Molander –…”

Section: Introductionsupporting

confidence: 78%

“…Since Tour and co‐workers demonstrated the first nickel‐catalyzed borylation of aryl halides, various Ni‐catalyzed borylation reactions of aryl halides based on [Ni(PR 3 ) 2 Cl 2 ] complexes were reported . A mixed‐ligand system developed by Percec and co‐workers consisting of [Ni(dppp)Cl 2 ] (dppp=1,3‐bis(diphenylphosphino)propane) and dppf as the co‐ligand turned out to be very efficient for the borylation of aryl chlorides –. Furthermore, this system, as well as [Ni(dppp)Cl 2 ] with PPh 3 (triphenylphosphine) as the additional ligand, turned out to be effective catalysts for the borylation of aryl iodides, bromides, and chlorides bearing electron‐rich and electron‐deficient ortho ‐substituents in toluene at 100 °C .…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, this system, as well as [Ni(dppp)Cl 2 ] with PPh 3 (triphenylphosphine) as the additional ligand, turned out to be effective catalysts for the borylation of aryl iodides, bromides, and chlorides bearing electron‐rich and electron‐deficient ortho ‐substituents in toluene at 100 °C . These borylation reactions involved the use of in situ prepared HBneop as the boron source formed by adding BH 3

\cdot

DMS (DMS=dimethylsulfide) to a toluene solution of neopentylglycol, as well as NEt 3 as an additive, which has to be freshly distilled from CaH 2 for a satisfying catalytic conversion –. In the same year, Murata et al.…”

Section: Introductionmentioning

confidence: 99%

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Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Kuehn

Jammal

Lubitz

et al. 2019

Chemistry A European J

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NHC-nickel( NHC = N-heterocyclic carbene) complexes are efficient catalysts for the CÀCl bond borylation of aryl chlorides using NaOAc as ab ase and B 2 pin 2 (pin = pinacolato) as the boron source.T he catalysts [Ni 2 (ICy) 4 (m-(h 2 :h 2 )-COD)] (1,I Cy = 1,3-dicyclohexylimidazolin-2-ylidene;C OD = 1,5-cyclooctadiene), [Ni(ICy) 2 (h 2 -C 2 H 4 )] (2), and [Ni(ICy) 2 (h 2 -COE)] (3,C OE = cyclooctene) comparew ell with other nickel catalysts reported previously for aryl-chloride borylation with the advantage that no further ligandsh ad to be added to the reaction. Borylation also proceeded with B 2 neop 2 (neop = neopentylglycolato)a st he boron source. Stoichiometrico xidative addition of different aryl chlorides to complex 1 was highly selectivea ffording trans-[Ni(ICy) 2 (Cl)(Ar)]

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Section: Introductionsupporting

confidence: 78%

Section: Introductionmentioning

confidence: 99%

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Section: Introductionmentioning

confidence: 99%

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Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Kuehn

Jammal

Lubitz

et al. 2019

Chemistry A European J

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“…In addition to the electron-withdrawing and electron-donating functionality demonstrated previously for the neopentylglycolborylation of aryl bromides341 and aryl iodides,341 other functionality such as cyano, ketone, methylcyano, phenylsulfone, and bisimide were effectively tolerated. Bisborylation of dichlorides347 or borylation of protic substrates provided incomplete or no conversion to product, respectively. (Scheme 97)…”

Section: Nickel-catalyzed Reactions Of Aryl and Vinyl Sulfonates Amentioning

confidence: 99%

Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds

et al. 2010

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“…The harsh reaction conditions used in the latter approach severely limit functional group incorporation into the boronic acid derivatives 5. Another common method makes use of bis(pinacolato)diboron or related reagents to access arylboronates catalytically according to Miyaura's widely used protocol 6–12. When boronic acids are the targets required in any of these protocols, the boronate esters must be converted by way of oxidation,13 hydrolysis,14 reduction,15 or transesterification 16.…”

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confidence: 99%

Palladium-Catalyzed, Direct Boronic Acid Synthesis from Aryl Chlorides: A Simplified Route to Diverse Boronate Ester Derivatives

2010

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Although much current research focuses on developing new boron reagents and identifying robust catalytic systems for the cross-coupling of these reagents, the fundamental preparations of the nucleophilic partners (i.e., boronic acids and derivatives) has been studied to a lesser extent. Most current methods to access boronic acids are indirect and require harsh conditions or expensive reagents. A simple and efficient palladium-catalyzed, direct synthesis of arylboronic acids from the corresponding aryl chlorides using an underutilized reagent, tetrahydroxydiboron B 2 (OH) 4 , is reported. To insure preservation of the carbon-boron bond, the boronic acids were efficiently converted to the trifluoroborate derivatives in good to excellent yields without the use of a workup or isolation. Further, the intermediate boronic acids can be easily converted to a wide range of useful boronates. Finally, a two-step, one-pot method was developed to couple two aryl chlorides efficiently in a Suzuki-Miyaura-type reaction.The Suzuki-Miyaura cross-coupling reaction has become of immense utility and thus importance,1 , 2 and yet there does not exist a simple, robust, catalytic, and functional group tolerant method that provides direct access to the boronic acid, with straightforward conversion to related derivatives. Thus, arylboronic acids are normally accessed by hydrolysis of boronate esters, and consequently many other boronic acid derivatives (e.g., organotrifluoroborates) are derived ultimately from these same boronate esters. The boronate esters can be accessed in a number of ways, including iridium-catalyzed C-H activation with bis(pinacolato)diboron3 and transmetalation from reactive organometallics.4 The harsh reaction conditions used in the latter approach severely limit functional group incorporation into the boronic acid derivatives.5 Another common method makes use of bis(pinacolato)diboron or related reagents to access arylboronates catalytically according to Miyaura's widely used protocol.6 -12 When boronic acids are the targets required in any of these protocols, the boronate esters must be converted by way of oxidation,13 hydrolysis,14 reduction, 15 or transesterification. 16 These methods are inherently inefficient both in terms of atom economy and step economy, employ harsh reaction conditions (NaIO 4 , aq HCl, LAH, diethanolamine, BBr 3 ), or require the use of excess polymer-supported boronic acid. 16,17 Further, the transformation of pinacol boronate esters to the analogous trifluoroborates often suffers from difficulties in purification, rendering these protocols exceedingly tedious. 18,19 In this communication, the development of the first direct synthesis of boronic acids via palladium-catalyzed cross-coupling of aryl chlorides with tetrahydroxydiboron B 2 (OH) 4 (1) is outlined. [20][21][22][23] This protocol allows the direct synthesis and isolation of arylboronic acids and also permits the preparation of trifluoroborates and diverse boronate analogs without the use of highly reactive organomet...

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Neopentylglycolborylation of Aryl Chlorides Catalyzed by the Mixed Ligand System NiCl₂(dppp)/dppf

Cited by 71 publications

References 29 publications

Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds

Palladium-Catalyzed, Direct Boronic Acid Synthesis from Aryl Chlorides: A Simplified Route to Diverse Boronate Ester Derivatives

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Neopentylglycolborylation of Aryl Chlorides Catalyzed by the Mixed Ligand System NiCl2(dppp)/dppf

Cited by 71 publications

References 29 publications

Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Stoichiometric and Catalytic Aryl−Cl Activation and Borylation using NHC‐stabilized Nickel(0) Complexes

Nickel-Catalyzed Cross-Couplings Involving Carbon−Oxygen Bonds

Palladium-Catalyzed, Direct Boronic Acid Synthesis from Aryl Chlorides: A Simplified Route to Diverse Boronate Ester Derivatives

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Neopentylglycolborylation of Aryl Chlorides Catalyzed by the Mixed Ligand System NiCl₂(dppp)/dppf