Nickel-catalyzed C–P cross-coupling reactions of aryl iodides with H-phosphinates

Kinbara, Atsushi; Ito, Momoko; Abe, Tohru; Yamagishi, Takehiro

doi:10.1016/j.tet.2015.07.073

Cited by 27 publications

(21 citation statements)

References 39 publications

(11 reference statements)

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“…the purification via chromatography) somewhat inefficient. However, it is worthy to mention that the difference between the outcome of the P-C couplings applying 1.1 or 1.2 equivalents of the Ph 2 P(O)H reagent is not significant ( [13][14][15][16][17][18][19]. To clarify the situation for our case, we wished to evaluate the mechanism of the Hirao reaction performed in the absence of a reducing agent, using NiX 2 (X=Cl or Br) as the catalyst precursor and some excess of the >P(O)H reagent as the P-ligand.…”

Section: Optimization Of the Nix 2 -Catalyzed Hirao Reaction Of >P(o)mentioning

confidence: 99%

“…This was checked in separate experiments irradiating the mixture of NiCl 2 and Ph 2 P(O) H or (EtO) 2 P(O)H (the former in acetonitrile solution) at 150 °C for 20 min or 45 min, respectively. On workup, the >P(O)H reagents were regenerated unchanged as suggested by the 31 P NMR chemical shifts and LC-MS. [13][14][15][16][17][18][19] exhibited a strongly exothermic transformation.…”

Section: The Mechanism Of the Ni(ii)-catalyzed Hirao Reactionmentioning

confidence: 99%

“…A part of the P-C couplings were performed using Ni(II) salts together with Zn or Mg as the reducing agent to form Ni(0) [12][13][14][15][16][17][18][19]. In a part of the cases P-ligands [12,19], in other instances N-ligands [13][14][15][16][17][18][19] were used to form the Ni complexes. The theoretical calculations [18] of Zhao and co-workers justified the involvement of Ni(0) in the usual catalytic cycle starting with oxidative addition of the, in this case, vinyl bromide reactant.…”

Section: Introductionmentioning

confidence: 99%

“…Mono-and bidentate P-ligands, such as PPh 3 , PCy 3 , or dppp, dppe, dppf, dppb, dcype and BINAP, respectively, were also applied together with NiCl 2 or Ni(COD) 2 [24][25][26][27][28][29][30][31][32][33][34][35]. When applying the Ni(acac) 2 and Ni(COD) 2 precursors, principally, the classical mechanism [13,18,19,[34][35][36] may work, however, the way of operation of Ni(II) salts in the absence of reductants is uncertain. In a special case, CeO 2 -or Al 2 O 3 -based Ni-nanoparticles were used in the P-C coupling of aryl halides and secondary phosphine oxides [37].…”

Section: Introductionmentioning

confidence: 99%

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A surprising mechanism lacking the Ni(0) state during the Ni(II)-catalyzed P–C cross-coupling reaction performed in the absence of a reducing agent – An experimental and a theoretical study

Henyecz

Mucsi

Keglevich

2019

Pure and Applied Chemistry

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The Hirao reaction, i.e. the P–C coupling between a bromoarene and a >P(O)H reagent performed in most cases in the presence of a Pd(0) complex incorporating a P-ligand may also be carried out applying a Ni(II) catalyst precursor with or without Zn or Mg as the reducing agent. The Ni catalysts may include P- or N-ligands. B3LYP/6-31G(d,p)//PCM(MeCN) quantum chemical calculations suggested that the mechanism of the NiX2 catalyzed (X=Cl or Br) P–C couplings performed in the absence of a reducing agent, and in the excess of the >P(O)H reagent serving as the P-ligand (via its tautomeric >POH form) is completely different from that of the Pd(OAc)2 promoted version, as no reduction of the Ni(II) occurs. In the two variations mentioned, the active catalyst is the dehydrobrominated species derived from primary complex [(HO)Y2P]2Ni(II)Br2, and the [(HO)Y2P]2Pd(0) complex itself, respectively. Both species undergo temporary oxidation (to “Ni(IV)” and “Pd(II)”, respectively) in the catalytic cycle. During the catalysis with “P2Ni(II)X2”, one of the P-ligands serves the >P(O)H function of the ArP(O)H < product. The consequence of this difference is that in the Ni(II)-catalyzed case, somewhat less >P(O)H-species is needed than in the Pd(0)-promoted instance. Applying 10 % of the Pd(OAc)2 or NiX2 precursor, the optimum quantity of the P-reagent is 1.3 equivalent and, in the first approach, 1.1 equivalent, respectively. Preparative experiments justified the new mechanism explored. The ligation of Ni(II) was also investigated by theoretical calculations. It was proved that the bis-complexation is the most favorable energetically as compared to the mono-, tri- and tetra-ligation.

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Section: Optimization Of the Nix 2 -Catalyzed Hirao Reaction Of >P(o)mentioning

confidence: 99%

Section: The Mechanism Of the Ni(ii)-catalyzed Hirao Reactionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A surprising mechanism lacking the Ni(0) state during the Ni(II)-catalyzed P–C cross-coupling reaction performed in the absence of a reducing agent – An experimental and a theoretical study

Henyecz

Mucsi

Keglevich

2019

Pure and Applied Chemistry

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“…The protocol was extended to H -phosphinates, as well as secondary phosphine oxides applying a wide range of arenes [ 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 , 21 , 22 ]. Later on, Ni- and Cu complexes were also used as catalysts [ 10 , 11 , 23 , 24 , 25 , 26 , 27 , 28 , 29 , 30 , 31 ]. Green chemical approaches, including microwave (MW)-assistance [ 32 , 33 , 34 , 35 , 36 , 37 ] and phase transfer catalysis, were also elaborated [ 38 , 39 , 40 , 41 ].…”

Section: Introductionmentioning

confidence: 99%

Focusing on the Catalysts of the Pd- and Ni-Catalyzed Hirao Reactions

2020

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The Hirao reaction involving the phosphinoylation or phosphonation of aryl halides by >P(O)H reagents is a P–C bond forming transformation belonging to the recently very hot topic of cross-couplings. The Pd- or Ni-catalyzed variations take place via the usual cycle including oxidative addition, ligand exchange, and reductive elimination. However, according to the literature, the nature of the transition metal catalysts is not unambiguous. In this feature article, the catalysts described for the Pd(OAc)2-promoted cases are summarized, and it is concluded that the “(HOY2P)2Pd(0)” species (Y = aryl, alkoxy) is the real catalyst. In our model, the excess of the >P(O)H reagent served as the P-ligand. During the less studied Ni(II)-catalyzed instances the “(HOY2P)(−OY2P)Ni(II)Cl−” form was found to enter the catalytic cycle. The newest conclusions involving the exact structure of the catalysts, and the mechanism for their formation explored by us were supported by our earlier experimental data and theoretical calculations.

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Catalyst‐ and Oxidant‐Free Desulfonative C−P Couplings for the Synthesis of Phosphine Oxides and Phosphonates

et al. 2017

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An efficient and practical approach towards phosphine oxides and phosphonates has been successfully developed through the desulfonative coupling of various sulfones with secondary phosphine oxides and phosphites. This protocol features simple experimental procedures under mild conditions (i. e., catalyst‐ and oxidant‐free, room temperature and open to air). By doing so, a variety of alkynyl, alkenyl and allyl phosphine oxides or phosphonates can be produced in generally good reaction efficiency and selectivity (31 examples, up to 98% yield).magnified image

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Nickel-catalyzed C–P cross-coupling reactions of aryl iodides with H-phosphinates

Cited by 27 publications

References 39 publications

A surprising mechanism lacking the Ni(0) state during the Ni(II)-catalyzed P–C cross-coupling reaction performed in the absence of a reducing agent – An experimental and a theoretical study

A surprising mechanism lacking the Ni(0) state during the Ni(II)-catalyzed P–C cross-coupling reaction performed in the absence of a reducing agent – An experimental and a theoretical study

Focusing on the Catalysts of the Pd- and Ni-Catalyzed Hirao Reactions

Catalyst‐ and Oxidant‐Free Desulfonative C−P Couplings for the Synthesis of Phosphine Oxides and Phosphonates

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