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. 2019 Jun;16(4):523–545. doi: 10.2174/1570179416666190415110834

New Developments on the Hirao Reactions, Especially from “Green” Point of View

Réka Henyecz 1, György Keglevich 1,*
PMCID: PMC7432197  PMID: 31984929

Abstract

Background:

The Hirao reaction discovered ca. 35 years ago is an important P–C coupling protocol between dialkyl phosphites and aryl halides in the presence of Pd(PPh3)4 as the catalyst and a base to provide aryl phosphonates. Then, the reaction was extended to other P-reagents, such as secondary phosphine oxides and H-phosphinates and to other aryl and hetaryl derivatives to afford also phosphinic esters and tertiary phosphine oxides. Instead of the Pd(PPh3)4 catalyst, Pd(OAc)2 and Ni-salts were also applied as catalyst precursors together with a number of mono- and bidentate P-ligands.

Objective:

In our review, we undertook to summarize the target reaction with a special stress on the developments attained in the last 6 years, hence this paper is an update of our earlier reviews in a similar topic.

Conclusions:

“Greener” syntheses aimed at utilizing phase transfer catalytic and microwave-assisted approaches, even under “P-ligand-free. or even solvent-free conditions are the up-to date versions of the classical Hirao reaction. The mechanism of the reaction is also in the focus these days.

Keywords: Hirao reaction, P-C coupling, Pd-catalyst, Phosphonates, Phosphinates, Phosphine oxides, Green synthesis

1. THE TRADITIONAL HIRAO REACTION

The Hirao reaction that is, a P-C coupling to furnish phosphonates or phosphine oxides, was reviewed 7 years ago by us [1, 2]. The purpose of this survey was to give an update on the newer developments. Of course, the most important precedents have also been summarized.

1.1. Palladium(0)-catalyzed Hirao Reactions

Hirao et al. described the first P-C coupling reaction between vinyl- or aryl halides and dialkyl phosphites in the presence of tetrakis(triphenylphosphine)palladium as the catalyst, applying organic bases in toluene as the medium, or without the use of any solvent (Scheme 1) [3-5].

Scheme 1.

Scheme 1

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Then, the Pd(PPh3)4-catalyzed Hirao reaction was extended to a number of cases. Beside dialkyl phosphites [6-22], H-phosphinates

[23-28] and secondary phosphine oxides [29-31] were also reacted with aryl- and vinyl halides, or sulfonates [31-36]. The most com-monly used bases were triethylamine and N, N-diisopropyl-ethylamine, but N-methyl morpholine was also used [24, 34]. The solvent may be toluene and THF [35], or dipolar aprotic solvents, e.g. acetonitrile [34, 37], DMF [33, 38] or DMSO [38]. The P-C coupling reaction of optically active H-phosphinates and alkylarylphosphine oxides proceeded with the complete retention of configuration [39-43].

1.2. P-C Coupling in the Presence of Metal Salts and Ligands

1.2.1. The use of Pd(II) Sources and P-ligands

The use of palladium-precursors (e.g. Pd(OAc)2, PdCl2 or even Pd(dba)2) in combination with mono- and bidentate P-ligands is more user-friendly than applying the sensitive and rather expensive Pd(PPh3)4. In this case, the active catalyst is formed in situ by reduction of the Pd(II) to Pd(0).

The generally accepted catalytic cycle of the Hirao reaction [44] is similar to the mechanism of the well-known Pd-catalyzed 
C-C couplings [45], as it follows the classic three steps (Scheme 2): the oxidative addition of the aryl (or vinyl) halide to the Pd0Ln to form an “Ar-PdIILn-X” complex (A). The next step is the ligand exchange, when the Y2P(O)H reagent enters the catalytic cycle and replaces the X- anion in the Pd(II) complex. Finally, the reductive elimination from species B leads to the desired product (2), while the active Pd(0) catalyst is regenerated.

Scheme 2.

Scheme 2

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Investigation of the reaction mechanism revealed that, the trivalent tautomeric form (Y2POH) of the Y2P(O)H reagent is involved in the change of ligands step [46, 47]. It should also be noted that the presence of PPh3 and added anions may make the ligand substitution and the whole catalytic cycle more complex [48].

Arylphosphonates (3), important building blocks of biologically active compounds [51, 55, 56], flame retardants [54] or catalyst ligands [66, 67] may be easily synthetized by the Hirao reaction of dialkyl phosphites with aryl halides or triflates (Scheme 3, Table 1).

Scheme 3.

Scheme 3

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Table 1. The synthesis of arylphosphonates using Pd(II) precursors and P-ligands.
Pd-precursor P-Ligand Base Solvent Reaction Conditions Ref.
Pd(OAc)2 PPh3 Et3N, Cy2MeN, iPr2EtN EtOH reflux, 16-68 h [49-56]
Cs2CO3 toluene 110 °C, 18 h [57]
Pd(OAc)2 PPh3, dppf, dppb, dppp, BINAP Et3N, iPr2NEt THF, MeCN, DMF, DMSO,
1,4-dioxane, toluene		 60-110 °C, 1.5-72 h [44, 58-66]
Pd(OAc)2, Pd(dba)2 dppb iPr2NEt, Et3N DMSO, toluene 25-100 °C, 12-72 h [66-70]
Pd(dppf)Cl2 iPr2NEt, Et3N MeCN, toluene 82-90 °C, 15-24 h [71,72]
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Several arylphosphonates were prepared in the presence of Pd(OAc)2 and the simplest P-ligand, PPh3 [49-57]. The addition of tetra-n-butylammoniumchloride, -bromide or -acetate as anionic additives could enhance the coupling reactions, when Pd(OAc)2 was used as the catalyst precursor and PPh3 as the ligand [44]. KOAc and NaOAc were also applied as ionic additives in the Hirao reaction [58-62]. In the presence of Pd(OAc)2 or Pd(dba)2 as the Pd precursor, dppf [58-65], dppb [58, 66-70], dppp [58] and BINAP [58] could also be used as ligands. Pd(dppf)2Cl2 was also a suitable catalyst to promote the coupling reaction of dialkyl phosphites [71, 72].

Using H-phosphinates as the reactant, both bromoarenes and less reactive chloroarenes were suitable substrates in the cross-coupling (Scheme 4) [47, 48, 73-75]. The reactions were performed using Pd(OAc)2 as the catalyst precursor and different ligands (PPh3, Xantphos, dppb, dppf, dppe, dppp, BINAP, DBFphos, PS-nixantphos), along with bases (iPr2NEt, pyridine, propylene oxide). The best results were obtained applying Xantphos [47, 48, 73], dppb [74] or dppf [75] as the P-ligand, and N,N-diisopro-pylethylamine as the base. Employing a solvent/co-solvent system was beneficial, as it may support the tautomerization of the P-reagent, and thus the ligand-exchange step of the catalytic cycle. The Hirao reaction of (R)-menthyl(hydroxymethyl)-H-phosphinate (R1 = menthyl, R2 = CH2OH) took place with the retention of the configuration at P [73].

Scheme 4.

Scheme 4

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An important and widely investigated Pd-catalyzed Hirao reaction is the coupling of aromatic species and secondary phosphine oxides, as valuable tertiary phosphines that can be applied as ligands in transition metal complexes can be formed by the reduction of the resulting phosphine oxides. It became clear that the Pd(OAc)2 - bidendate ligand (dppp or dppb) system has a high tolerance for functional groups (Scheme 5) [76-81]. During the preparation of various P-containing ligands, the phosphorylation 
of 2-bromobenzaldehyde [76], 2-(2-bromophenoxy)tetrahydro-
2H-pyran [77] and 2’-iodo-6,6’-dimethoxy-N,N-dimethyl-[1,1’-biphenyl]-2-amine [78] with diarylphosphine oxides took place in moderate to good yields (37-92%). The selective substitution of the iodide group of 3-bromoiodobenzene could be achieved in rather a good yield (65%) [79]. The cross-coupling of sterically hindered dibromo-3-spirobis(indene) [80] and a dinoflate bis carbazole derivative [81] with diphenylphosphine oxide took also place with high selectivity.

Scheme 5.

Scheme 5

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BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) can be considered as the most powerful, and one of the most commonly used bidentate chiral ligands in asymmetric catalysis [82]. In the synthesis of BINAP derivatives (6), the reaction of axial chiral triflates and diaryl or dialkyl phosphine oxides is most often carried out applying Pd(OAc)2 as the Pd precursor and iPr2NEt [83-102, 104-107] or Na2CO3 [103] as the base in DMSO (Scheme 6). Both the (R) and (S) binaphyl structures could be functionalized in different ways. In the case of binaphthyl bistriflates, the selective phosphorylation of only one triflate unit was possible [83-93]. Hence, the bis-phosphonylation could not be realized, and a “bypass” procedure had to be developed for the preparation of bisphosphines: after the mono-phosphonylation, the resulting phosphine oxide was reduced with a silane and then the second cross-coupling took place [100-103]. Heterocyclic analogs of BINAP as potential catalysts of new enantioselective approaches, such as biaryl isoquinolines (called Quinazolinaps) [104, 105], 1-aryl-3,4-dihydroisoquinolines (DHIQs) [106] and a new class of naphthyl-indole heterobiaryl skeletons [107] were also developed.

Scheme 6.

Scheme 6

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Synthesis of the representatives of other, even more complex aromatic tertiary phosphine oxides (7) is shown in Scheme 7 [108-127]. The coupling reaction of sterically hindered substrates means a real challenge and usually requires long reaction times. Despite the difficulties, selective mono- [108, 120-122], double [108, 111, 113, 125-127] and quadruple [125-127] phosphorylations could be achieved.

Scheme 7.

Scheme 7

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Beside Pd(OAc)2, tris(dibenzylideneacetone)dipalladium(0) is also a suitable catalyst for P-C coupling reactions to afford tertiary phosphine oxides. A general method was developed for the reaction of aryl iodides and dialkyl-, alkylaryl- or diarylphosphine oxides in the presence of Pd2(dba)3 and Xantphos using triethylamine as the base (Scheme 8) [128].

Scheme 8.

Scheme 8

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(2-Bromophenyl)diphenylphosphine oxide (9) could be synthetized in a yield of 65% from 2-bromoiodobenzene by applying Pd2(dba)3 as the catalyst, and dppp as the P-ligand in toluene (Scheme 9) [129].

Scheme 9.

Scheme 9

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A series of intermediates for P-ligands were synthesized by the reaction of aryl triflates and diaryl phosphine oxides using Pd2(dba)3 (Scheme 10) [130-136]. The selective transformation of the triflate group of 2-bromophenyl trifluoromethanesulfonate [130], 2-bromo-4-methoxyphenyl trifluoromethanesulphonate [131] and 1-bromonaphthalen-2-yl trifluoromethanesulfonates [132-134] could be achieved in the presence of a dppp ligand and Hünig-base in toluene. (1-(Naphtho [2,3-b]furan-9-yl)naphthalen-2-yl)diaryl-phosphine oxides were obtained by similar cross-coupling reactions employing dppb as the ligand and DMSO as the solvent [135]. A double P-C coupling of 5,5'-diamino-(1,1’-biphenyl)-2,2'-diyl bis(trifluoromethanesulfonate) with diphenylphosphine oxide via N-Boc-protection and acidic cleavage resulted in the corresponding product in a 20% overall yield [136].

Scheme 10.

Scheme 10

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Finally, methods are summarized that apply other substrates other than aryl halides or triflates. Fu et al. reported a convenient method for the coupling reaction of aryl tosylates or mesylates and dialkyl phosphites or ethyl phenyl-H-phosphinate. The best results were obtained using Pd(OAc)2 as the catalyst with CM-Phos as the ligand and DIPEA as the base (Scheme 11) [137].

Scheme 11.

Scheme 11

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Chinese researchers described the Pd-catalyzed reactions of dialkyl phosphites and aryl imidazolyl sulfonates (Scheme 12) [138]. The reaction has a high tolerance of functional groups, although it cannot be regarded as an atom-efficient approach.

Scheme 12.

Scheme 12

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Arylboronic acids were reacted with diphenylphosphine oxide, ethyl phenyl-H-phosphinate or diethyl phosphite. The best results were obtained applying the Pd(OAc)2-dppb system as the catalyst (Scheme 13) [139].

Scheme 13.

Scheme 13

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The desulfitative cross-coupling reaction of sodium benzenesulfinate and dialkyl phosphites was performed in the presence of silver carbonate as the oxidant, and tetrabutyl-ammonium chloride (TBAC) as an additive (Scheme 14) [140]. The role of Ag2CO3 has not been clarified.

Scheme 14.

Scheme 14

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1.2.2. Nickel(II)-catalyzed Hirao Reactions

Beside the widely-used Pd catalysts, the cheaper Ni-precursors in combination with P- and N-ligands may also be used. However, this field is much less investigated. There are a few examples utilizing a Ni(II) precursor - ligand system. During the arylation of dimethyl phosphite and diphenylphosphine oxide, NiCl2 was combined with P-ligands (PPh3 or dppp) (Scheme 15) [141, 142].

Scheme 15.

Scheme 15

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The reaction of aryl boronic acids and >P(O)H reagents was performed in the presence of Ni(II) salts and N-ligands (Scheme 16) [143].

Scheme 16.

Scheme 16

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The coupling of aryl halides, mesylates and tosylates with >P(O)H species using Ni(II)-precursors and dppp or N-ligands and zinc dust led to the formation of triarylphosphine oxides, aryl-phosphonates and aryl-phosphinates (Scheme 17) [144, 145]. According to the authors, the zinc powder was required for the reduction of Ni(II) to Ni(0).

Scheme 17.

Scheme 17

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1.2.3. Environmental-friendly Approaches

Over the past few years, “green” techniques including phase transfer catalysis (PTC) and microwave (MW) irradiation came into fashion.

The PTC-promoted Hirao reaction employing triethylbenzyl-ammonium chloride (TEBAC) was developed by Beletskaya et al. (Scheme 18) [146-149]. The reaction of diethyl phosphite and bromoarenes performed in the presence of Pd(OAc)2 gave better results using tris(2-furyl)phosphine as the P-ligand, as compared to the case applying triphenylphosphine [146, 147]. 6-Aryl-6H-dibenzo[c,e][1,2]oxaphosphorine 2-oxides were prepared by both Pd- and Ni-catalyzed PTC-assisted coupling reactions [148]. It is noteworthy that the solid-liquid phase coupling of “phosphorylated” monosaccharides could also be performed under PTC conditions [149].

Scheme 18.

Scheme 18

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The use of the MW technique in organic chemistry has spread. In this way, the yields and selectivity could be improved, the needless excess of reagents could be eliminated, and the catalytic-systems could be simplified [150]. In 1997, a Pd(PPh3)2Cl2-catalyzed P-C coupling reaction performed in a Teflon autoclave placed in a kitchen MW oven was reported [151]. Ten years later, Stawinski et al. developed a general MW-assisted method for the 
P-C coupling of dialkyl phosphites and substituted aryl, hetaryl and vinyl reagents in the presence of Pd(PPh3)4 as the catalyst, Cs2CO3 as the base, and THF as the solvent using a dedicated MW oven (Scheme 19) [152].

Scheme 19.

Scheme 19

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Later on, the reaction of a wide range of substrates was carried out under MW irradiation. For example, the coupling of aryl boronic acids or aryltrifluoroborates and dialkyl phosphites was performed employing Pd salts as the catalyst precursor and dmphen as the ligand (Scheme 20) [153].

Scheme 20.

Scheme 20

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Water-soluble tertiary phosphine oxides were prepared by the Pd/C catalyzed coupling reaction of halobenzoic acids and diphenylphosphine oxide in water (Scheme 21) [154].

Scheme 21.

Scheme 21

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2. NOVEL DEVELOPMENTS ON THE HIRAO REACTION

Extensions and novel advances on the Hirao reaction attained in the last four years are presented in this chapter.

2.1. Extensions of the Pd-catalyzed Hirao Reaction

Optically active P(V) derivatives, the precursors of P(III) ligands are of importance. Beside resolution [155], enantioselective syntheses may also lead to optically active phosphine oxides [156-158]. Transition-metal-catalyzed cross-coupling reactions may also be suitable for the preparation of optically active phosphine oxides. The Pd(PPh3)4-catalyzed coupling of aryl halides and enantio-merically pure tert-butylphenylphosphine oxide carried out in the presence of K2CO3 as the base and toluene as the solvent afforded enantiomerically enriched (ee>78%) tertiary phosphine oxides in yields of 63-96% (Scheme 22) [159].

Scheme 22.

Scheme 22

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(S)-Tert-butyl-aryl phosphine oxides were coupled with 2-bromopyridine using Pd2(dba)3 as the catalyst, dppp as the ligand, and DBU as the base to give products 13 with excellent selectivity (ee>97%) (Scheme 23) [160]. The retention of the P-atom was proved by single-crystal X-ray analysis.

Scheme 23.

Scheme 23

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Stankevič et al. prepared the m-anisyl-t-butyl-p-tolylphosphine oxide (14) by the Pd(PPh3)2Cl2-catalyzed reaction of t-butyl-p-tolylphosphine oxide and 3-bromoanizole (Scheme 24) [161].

Scheme 24.

Scheme 24

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The palladium-catalyzed Hirao reaction was extended to the phosphorylation of aryl amides (Scheme 25) [162]. Substrates containing acyclic and cyclic N-activating groups were reacted with dialkyl phosphites. Mechanistic studies suggested that the course of the reaction is similar to that of the original Hirao reaction of aryl halides, and the key step of the catalytic cycle is the insertion of the metal into the C-N bond.

Scheme 25.

Scheme 25

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A method for the arylation of P-stereogenic secondary phosphine oxides was developed to provide optically active tertiary phosphine oxides (15) (Scheme 26) [163]. The P-C coupling of ortho-substituted aryl iodides carried out applying Pd(CF3CO2)2 as the precursor for Pd(0) and a chiral ligand (L*) furnished the target tertiary phosphine oxides (15) in moderate to good enantio-selectivities (ee: 19-83%).

Scheme 26.

Scheme 26

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Chinese researchers reported a protocol for the P-C coupling of heteroaryl boronic acids and dialkyl phosphites in the presence of PdCl2 and PPh3, and in the absence of any base (Scheme 27) [164]. At the same time, Ag2O was needed as an additive, whose role has not been clarified.

Scheme 27.

Scheme 27

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Arylphosphonates (3) were prepared via C-Si bond cleavage by the reaction of arylsilanes and dialkyl phosphites performed in the presence of Pd(PPh3)Cl2 as the catalyst (Scheme 28) [165]. Potassium fluoride is necessary to activate the arylsilane before its entering the catalytic cycle. Ag2CO3 was assumed as a reoxidant at the end of the catalytic cycle, however, this has not been proved.

Scheme 28.

Scheme 28

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New magnetically recoverable heterogeneous palladium catalysts were developed to make the Hirao reaction environ-mentally more capable (Scheme 29) [166-168]. At first, the Pd complex of an “NNN” princer ligand (BIP) supported on nanomagnetic γ-Fe2O3@SiO2 was prepared, which proved to be a good catalyst in the cross-coupling reaction of diethyl phosphite and iodobenzene under solvent-free conditions [166]. The Pd complex of 2-aminothiophenol (Pd-2-ATP-γ-Fe2O3) [167] and DABCO (Pd-DABCO-γ-Fe2O3) [168] could be used as a catalyst in pure water, or in sodium dodecyl sulfate (SDS) aqueous micellar solution. The heterogeneous catalysts could be reused in five or six consecutive cycles, without any significant loss in their catalytic activity.

Scheme 29.

Scheme 29

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2.2. Nickel-catalyzed P-C Coupling Reactions

In the last years, the Ni-catalyzed P-C bond formation was also developed. Han and his co-workers elaborated the P-arylation of different >P(O)H compounds with aryl triflates in the presence of Ni(cod)2 as the Ni(0) precursor and dppf as the P-ligand (Scheme 30) [169].

Scheme 30.

Scheme 30

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The same research group also used aryl pivalates as C-O bond activated substrates for coupling reactions with >P(O)H reagents (Scheme 31) [170, 171]. Application of the Ni(cod)2/dcype catalyst system led to the corresponding P=O derivatives (10) in good yields (50-98%). Beside phenol esters, benzylic and allylic esters could also be phosphorylated.

Scheme 31.

Scheme 31

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The combination of Ni- and photoredox catalysis allowed the cross-coupling of “C-O-S” containing aryl- and vinyl compounds (tosylates, sulfonates and sulfamates) with >P(O)H reagents under mild conditions (Scheme 32) [172]. In this case, Ni(cod)2 applied together with N-ligands, eg. 1,10-phenanthroline or dtbbyp, served as the catalyst.

Scheme 32.

Scheme 32

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The use of Ni(cod)2 as the Ni-source, and 8-hydroxyquinoline as the N-ligand allowed the synthesis of tertiary phosphine oxides

(19) from aryl nitriles and secondary phosphine oxides (Scheme 33) [173].

Scheme 33.

Scheme 33

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The coupling of amides with dialkyl phosphites described in subchapter 2.1, Scheme 25 was also accomplished using Ni(dppp)Cl2 as the catalyst (Scheme 34) [162].

Scheme 34.

Scheme 34

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An example for the application of Ni(OAc)2 together with a tiophene-based diphosphine ligand (dcypt) using the esters of aromatic carboxylic acids as the substrate is shown in Scheme 35 [174]. Utilizing NaF as an additive increased the efficiency of the coupling, although its exact role is unknown.

Scheme 35.

Scheme 35

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According to a recent study, the Ni-catalyzed P-C coupling reaction of aryl bromides and dialkyl phosphites was performed under electrochemical conditions to provide the corresponding aryl phosphonates (3) in moderate to good yields (15-91%) (Scheme 36) [175].

Scheme 36.

Scheme 36

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2.3. Copper-catalyzed P-C Couplings

The application of Cu as the catalyst is by far less investigated, thus it is a more challenging field. Cu-catalyzed methods for C-P bond formation were summarized in a recent review [176]. Since then, just a few methods have been described for the coupling of >P(O)H reagents and aryl halides using Cu(I) or Cu(II) precursors and N-ligands [177-182]. A novel method involves the reaction of aryl boronic acids and dialkyl phosphites performed in the presence of a Cu(II) complex, (Benz-bpa)Cu(CF3SO3)2 as the catalyst, and KOAc as an additive (Scheme 37) [183].

Scheme 37.

Scheme 37

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The enantioselective Cu-catalyzed P-C coupling reactions represent a new trend (Scheme 38) [184]. Optically active tertiary phosphine oxides (20) could be prepared from racemic secondary phosphine oxides and diaryliodonium tetrafluoroborate salts in the presence of Cu(II) triflate as the metal source, (S,S)-PhPyBox as the chiral N-ligand, and K2HPO4 as the base in acetonitrile-water mixture, in mostly high enantioselectivities (ee: 50-98%). The role of water has not been mentioned.

Scheme 38.

Scheme 38

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2.4. Other Methods

Special catalytic systems have also been developed. Visible light photoredox catalysis was combined with an Au catalyst to promote the reaction of aryldiazonium salts with H-phosphinates and H-phosphonates (Scheme 39) [185]. In this way, the reactions could be carried out at room temperature, without the addition of any base. However, the synthesis of the starting diazonium salts from commercially available anilines means an extra step.

Scheme 39.

Scheme 39

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A similar Au(I)-assisted redox catalytic coupling using diethyl phosphite and aryldiazonium salts was also developed (Scheme 40) [186]. In this case, 3-chloropyridine served as the base.

Scheme 40.

Scheme 40

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3. HIRAO REACTIONS WITHOUT THE ADDITION OF USUAL P-LIGANDS

Keglevich and his co-workers found that the Hirao reaction of bromoarenes with dialkyl phosphites, H-phosphinates or secondary phosphine oxides may take place without the addition of usual P-ligands, but using the >P(O)H reactant in excess under MW conditions (Scheme 41) [187, 188]. It was found that both electron-donating and electron-withdrawing substituents of the aromatic ring decrease the reactivity dictating harsher reaction conditions (175-200°C).

Scheme 41.

Scheme 41

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Our assumption was that in the Pd(OAc)2-catalyzed “P-ligand-free” Hirao reactions the trivalent tautomeric form of the excess of the >P(O)H reactant may serve as the P-ligand. To justify this, the reaction of bromobenzene with diethyl phosphite and diphenyl-phosphine oxide was investigated in detail (Scheme 42) [189].

Scheme 42.

Scheme 42

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Experiments showed that the use of only 1 equivalent of diethyl phosphite or diphenylphosphine oxide was not enough, as the yields were only 54% (24a) and 54% (24b), respectively. In the presence of 10% of Pd(OAc)2, the optimal amount of the >P(O)H reagent was 1.3 equivalents, leading to yields of 74% (24a) and 84% (24b), respectively. Theoretical calculations were in accord with the preparative results, and suggested that the >P(O)H reagents have a triple role in the cross-coupling process: 1 equivalent of it serves as the reactant, 10% of the >P(O)H species ensures the reduction of Pd(II) to Pd(0), while 20% of the reagent provides the P-ligand of the Pd-complexes of type (HO)Y2P…Pd…PY2(OH).

The formation of the active catalyst (PdP2) in the Hirao reaction of bromobenzene and diaryl phosphine oxides was studied in detail (Scheme 43). Quantum chemical calculations revealed that the activity of the PdP2 catalyst has a greater impact on the P-C coupling, than the intrinsic reactivity of the Ar2P(O)H compound. Hence, the catalyst containing (2-MeC6H4)POH as the ligand is more efficient, than that with Ph2POH ligand [190].

Scheme 43.

Scheme 43

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Later on, Hirao et al. have also studied a “P-ligand-free” P-C coupling reaction. Diethyl (4-methoxy-3-nitrophenyl)phosphonate (26) was synthetized from 4-bromo-1-methoxy-2-nitrobenzene applying only Pd(OAc)2 as the catalyst, and Na2CO3 as the base in xylene as the medium (Scheme 44) [191].

Scheme 44.

Scheme 44

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Recently, 2- and 4-phosphonated 13α-estrones (27 and 28) have been prepared by MW-assisted P-C coupling reactions [192]. Although the best results (yields of 66-93%) were obtained in the presence of Pd(PPh3)4, Pd(OAc)2 together with the excess of the Y2P(O)H reagent could also be used as the catalyst (to afford yields of 58-77%) (Scheme 45). The products proved to be potent estron-based OATP2B1 inhibitors.

Scheme 45.

Scheme 45

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A “ligand-free” MW-promoted desulfitative coupling of arylsulfinate salts with dialkyl phosphites was performed using PdCl2 as the catalyst under MW irradiation (Scheme 46) [193]. Ag2CO3 was assumed to be involved in the oxidation of the arylsulfinate substrate, but this has not been proved.

Scheme 46.

Scheme 46

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The Keglevich group also developed a Ni-catalyzed “P-ligand-free” P-C coupling process (Scheme 47) [194]. During the arylation of the >P(O)H compounds, NiCl2 was applied as the catalyst and triethylamine or potassium carbonate as the base under MW irradiation.

Scheme 47.

Scheme 47

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The coupling of aryl sulfides, sulfoxides or sulfones with >P(O)H reagents was carried out in the presence of Ni(cod)2 without the use of conventional ligands (Scheme 48) [195]. The reaction of diphenylphosphine oxide and thioanisol could be catalyzed by NiCl2.

Scheme 48.

Scheme 48

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A heterogeneous Ni-catalyst supported by CeO2 or Al2O3 was utilized in the P-C coupling of aryl halides and secondary phosphine oxides without any added ligand (Scheme 49) [196]. However, the catalyst used in the reaction of 1-bromonaphthalene and diphenylphosphine oxide, and separated from the mixture by filtration practically lost its activity in the second load.

Scheme 49.

Scheme 49

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Chinese researchers published the Cu-catalyzed “ligand-free” coupling reaction of >P(O)H compounds and aryl bromides or iodides to give the 2-phosphorylated phenolic derivatives (28) (Scheme 50) [197]. The reaction of (-)-menthyl phenylphosphinate and (-)-menthyl benzylphosphinate occurred with the retention of configuration at the P-atom. According to the plausible mechanism, the oxidative addition may take place via a “Cu-phenolate” intermediate, although the mechanism was not proved.

Scheme 50.

Scheme 50

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The reaction of vinyl or aryl halides with dialkyl phosphites was studied by applying excess of Cu(I)-iodide and the base (Scheme 51) [198]. The best results (yields of 78-99%) could be obtained in the presence of KH/HMPA system, but the results with triethylamine as the base and THF as the solvent also deserve attention providing product 1 in yields of 24-76%.

Scheme 51.

Scheme 51

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A Co-catalyzed and Cu-assisted P-C coupling of aryl/vinyl bromides and dialkyl phosphites or diphenylphosphine oxide was also described in the absence of any added ligand (Scheme 52) [199]. The corresponding products (2 and 31) were obtained in good yields (60-91%). The authors suggested that Co(I) formed from Co(II) by reduction with acac in the first step of the catalytic cycle may be the active form. At the same time, the transmetallation step is supported by Cu(I). It is noteworthy that the >P(O)H reactant was used in excess, so the participation of the >POH form cannot be excluded in the process.

Scheme 52.

Scheme 52

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Regarding the Ni-, Cu- or even the co-catalyzed “ligand-free” coupling protocols, it should be emphasized that these reactions may be of a complex nature, therefore further investigations are necessary to understand the mechanism of each system.

Nowadays, metal-free catalysis is of great importance. For this purpose, the P-C coupling of diaryl phosphine oxides with iodo-, or bromobenzoic acids was performed in the absence of any catalyst in water as the solvent under MW conditions (Scheme 53) [200]. Unfortunately, this method is limited only to the reaction of halobenzoic acids, but may be regarded as the “greenest” accomplishment that has been so far elaborated.

Scheme 53.

Scheme 53

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CONCLUSION

These days, the Hirao reaction is an important synthetic tool to provide phosphonates, phosphinates and tertiary phosphine oxides as useful intermediates. Toluene, DMSO, acetonitrile, 1,4-dioxane, THF, DMF, EtOH (or other alcohols) are the typical solvents used in the Hirao reaction. The selection of the solvent should also depend on the catalyst/catalyst precursor. Pd(PPh3)4 is, in most cases, applied together with toluene, while with Pd(OAc)2 as the catalyst precursor, DMSO is the most often used solvent. The best medium for the Ni-catalyzed P-C couplings is 1,4-dioxane, and sometimes acetonitrile. One can see that mainly aprotic solvents are applied, but protic solvents may also emerge. Both organic and ionic bases may be used in the Hirao reaction. Regarding the Pd-catalysts, triethylamine and diisopropylethylamine are the most often used tertiary amines, but the use of pyridine, DBU and N-methylmorpholine was also described. In certain cases, K2CO3, Cs2CO3 and Na2CO3 played the role of the deprotonating agent. In the Ni-catalyzed cases, all bases mentioned were used. The originally applied Pd(PPh3)4 catalyst may be replaced by Pd(OAc)2 used together with mono- and bidentate P-ligands. The best protocol is when the >P(O)H reagent serves not only as the reactant, but, via its tautomeric form (>P-OH), also as the P-ligand. In this “green” approach, the >P(O)H species have to be measured in a suitable excess (in three equivalents to the catalyst precursor), and MW-assistance is needed. The optimum temperature may be in the range of 120-150 °C. Ethanol and acetonitrile may be the best solvents, but in special cases, there is no need for any solvent. Triethylamine seems to be the best base. Other metals, such as Ni and Cu may also be used as catalysts. The environmentally-friendly variations of the P-C coupling reactions offer newer possibilities. Evaluation of the mechanism of the Hirao reaction has had a positive impact on finding the optimum conditions. The reactivity of the Hirao reaction is, of course, influenced by the substituent in the aromatic ring. Both the electron-donating and the electron-withdrawing groups decrease the reactivity. On the other hand, the P-C coupling reactions remained chemoselective also in the presence of different substituents, like halogeno-, ethoxycarbonyl- and acetyl groups.

ACKNOWLEDGEMENTS

Declared none.

LIST OF ABBREVIATIONS

graphic file with name COS-16-523-ls.jpg

CONSENT FOR PUBLICATION

Not applicable.

FUNDING

This work was sponsored by the National Research Development and Innovation Fund (K119202). Réka Henyecz was supported through the New National Excellence Program of the Ministry of Human Capacities (ÚNKP-18-3-I-BME-118).

CONFLICT OF INTEREST

The authors confirm that this article content has no conflict of interest.

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