Ni-catalyzed construction of C–P bonds from electron-deficient phenols via the in situ aryl C–O activation by PyBroP

Zhao, Yu‐Long; Wu, Guo‐Jie; Han, Fu‐She

doi:10.1039/c2cc31718d

Cited by 102 publications

(28 citation statements)

References 33 publications

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“…A series of aryl/vinyl boronates/iodides/sulfonates/nitriles were reacted with secondary phosphine oxides or dialkyl phosphites in the presence of Ni(II) salts, Ni(acac) 2 or Ni(COD) 2 together with mono-or bidentate N-ligands [20][21][22][23]. 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.…”

Section: Introductionmentioning

confidence: 99%

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: Introductionmentioning

confidence: 99%

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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“…Such a process could be possible by the in situ conversion of arenols into activated forms such as sulfonates or phosphonium [104,105] through the addition of stoichiometric amounts of activating reagents. Because of space limitations, this section only deals with the nickel-catalyzed direct transformation of arenols using non-classical stoichiometric activating reagents.…”

Section: Cross-coupling Reactions Of Arenolsmentioning

confidence: 99%

Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C–O Bond Activation

2016

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Nickel-catalyzed cross-coupling reactions of aryl esters, carbamates, carbonates, ethers and arenols are reviewed. Carbon-oxygen bonds in these phenol derivatives cannot be activated by palladium, a typical cross-coupling catalyst, but a low valent nickel species in conjunction with a strong σ-donor ligand is uniquely effective for achieving this. The review is organized primarily by substrate class and secondarily by coupling partners, encompassing organometallics, heteroatom nucleophiles, C-H bonds and many others. Although the reactions in this category are covered thoroughly, each reaction is described only briefly, so that it is possible to quickly overview the spectrum of nickel-catalyzed cross-coupling reactions of inert phenol derivatives. The robustness of inert phenol derivatives under typically used catalytic conditions as well as their utility as a directing group allow unique synthetic applications of these new C-O cross-coupling reactions, which is also included in cases where appropriate. Mechanistic aspects of C-O bond activation by nickel are also summarized, highlighting their diversity compared with the C-X bond activation involved in conventional cross-coupling processes.

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“…The method involves activation of a phenol with bromotripyrrolidinophosphonium hexafluorophosphate (PyBroP), followed by Ni-catalyzed coupling with H-phosphonate Scheme 23 Nickel-catalyzed coupling of H-phosphonates with aryl bromides [150] diesters or diaryl phosphine oxides [155]. The reaction can be carried out as a one-pot procedure without the need for isolating the activated phenol intermediate.…”

Section: Cu- Ni- and Other Metal-catalyzed Reactionsmentioning

confidence: 99%

Recent Advances in H-Phosphonate Chemistry. Part 2. Synthesis of C-Phosphonate Derivatives

Sobkowski

Kraszewski

Stawiński

2014

Phosphorus Chemistry II

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This chapter provides an overview of recent advances in the development of new methods and protocols for the formation of the P-C bond using H-phosphonate diesters as starting materials. Various chemical and stereochemical aspects of the transition metal-catalyzed cross-coupling and organocatalyst-promoted reactions which are relevant to the synthesis of structurally diverse C-phosphonate derivatives are surveyed.

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Ni-catalyzed construction of C–P bonds from electron-deficient phenols via the in situ aryl C–O activation by PyBroP

Cited by 102 publications

References 33 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

Nickel-Catalyzed Cross-Coupling Reactions of Unreactive Phenolic Electrophiles via C–O Bond Activation

Recent Advances in H-Phosphonate Chemistry. Part 2. Synthesis of C-Phosphonate Derivatives

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