Tetraphenylantimony carboxylates in the cascade Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxide

Moiseev, D. V.; Morugova, V. A.; Gushchin, A. V.; Shavirin, Andrey S.; Kursky, Yury A.; Dodonov, V. A.

doi:10.1016/j.jorganchem.2003.11.025

Cited by 31 publications

(8 citation statements)

References 19 publications

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“…[21] These cross-coupling reactions of arylantimony compounds with arylboronic acids or alkynes smoothly proceed in the absence of base reagents and copper cocatalysts. Pentavalent organoantimony(V) compounds could be also used as psedo-arylhalides for Pdcatalyzed CÀ C(Ar) bond formation in Heck-, [22][23][24] Stille-, [25] and Hiyama-type reactions. [26] Based on these knowledges, we initially focused on achieving the Pd catalyzed CÀ H arylation of benzothiophene (1 a) using organoantimony or bismuth compounds 2 a-9 ( Table 1).…”

Section: Resultsmentioning

confidence: 99%

“…2,5-Dimethylthiophene also afforded βphenylated product (23) in moderate yield. Furthermore, 3substituted thiophenes were treated with 2 a to give the corresponding products (24)(25)(26) in satisfactory yields. The reaction of 2 a with 2-and 3-acetylthiophenes, and 2-iodothiophene, and thiophene gave a complex mixture under these conditions (data not shown).…”

Section: Resultsmentioning

confidence: 99%

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Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

et al. 2018

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Regioselective CÀ H arylation using pentavalent organoantimony compounds as a new class of arylating reagents is described. The reaction of thiophenes with triarylantimony difluorides in the presence of 5 mol% of PdðOAcÞ 2 and 2 equiv. CuCl 2 at 80°C under aerobic conditions afforded the β-arylated thiophene derivatives in moderate-to-high yields. The reaction is sensitive to the electronic nature of the triarylantimony difluorides -those bearing an electron-donating group on the phenyl ring showed higher reactivity than those have an electron-withdrawing group. Scheme 1. Arylating reagents (ArÀ X) for Pd-catalyzed β-selective CÀ H arylation of thiophenes.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

et al. 2018

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“…Triarylantimony dicarboxylates act as effective arylating agents in Pd-catalyzed C-C(Ar) bond formation reactions such as [28][29][30] 31) and Hiyama-type 32) reactions. Over the past few years, we have also found that they are an efficient aryl donors in base-free Suzuki-type reactions and copper-and base-free Sonogashira-type reactions.…”

Section: The Reaction Of Triarylantimony Diacetates [Ar 3 Sb(oac) 2 ]mentioning

confidence: 99%

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Matsumura

Dong

Kakusawa

et al. 2015

CHEMICAL & PHARMACEUTICAL BULLETIN

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The reaction of triarylantimony diacetates [Ar 3 Sb(OAc) 2 ] with dialkyl H-phosphites [H-PO(OR)2] in the presence of a Pd(PPh 3 ) 4 (5 mol%) catalyst led to the formation of arylphosphonates in moderate to excellent yield under base-free conditions. This reaction is the first example of carbon-phosphorus bond formation by using an organoantimony compound as a pseudo-halide.Key words Hirao-type P-arylation; triarylantimony diacetate; arylphosphonate; dialkyl H-phosphite; basefree reaction Phosphorus-carbon (P-C) bond formation for the synthesis of organophosphorus compounds is a fundamental and significant research topic in organic synthesis, materials, and biology.1-6) Among these, the transition-metal-catalyzed crosscoupling reaction is one of the most practical methods in modern organic syntheses. [7][8][9] With regard to the synthesis of arylphosphonates, the Pd-catalyzed cross-coupling reactions of aryl halides with dialkyl H-phosphites (i.e., Hirao P-arylation) have proved to be a powerful method. [10][11][12][13][14][15][16][17][18][19][20][21] The general procedure of these P-arylations involves a Pd-phosphine complex as the catalyst with the use of a stoichiometric or an excess amount of a base. Recently, different aryl substances were investigated for their reactivity with phosphorus agents. Sulfonates, 22,23) diaryliodonium salts, 24) arylboronic acids, 25) aryldiazonium salts, 26) and triarylbismuthanes 27) have been reported to be useful for P-C bond formation as the arylating reagents with dialkyl H-phosphites; however, a base and/or an additive was required for the transformation.On the other hand, Pd-catalyzed cross-coupling reactions using organoantimony compounds have recently been the focus of attention. Triarylantimony dicarboxylates act as effective arylating agents in Pd-catalyzed C-C(Ar) bond formation reactions such as [28][29][30] 31) and Hiyama-type 32) reactions. Over the past few years, we have also found that they are an efficient aryl donors in base-free Suzuki-type reactions and copper-and base-free Sonogashira-type reactions. [33][34][35] Moreover, base-free Miyaura-type cross-coupling reactions for boron-carbon (B-C) bond formation using triarylantimony diacetates and tetra(alkoxo) diborons afforded the corresponding arylboronates.36) As a continuation of our studies on heteroatom-carbon bond formation, we now report a novel Pd-catalyzed Hirao-type P-arylation of a pentavalent organoantimony compound, triarylantimony diacetate, with dialkyl H-phosphites afford to the corresponding arylphosphonates without using any base. Results and DiscussionWe initially focused our attention on the determination of the optimum conditions for the P-arylation of organoantimony(V) and bismuth(V) compounds (1a-8) with diethyl phosphite (9a) without using a base. The results including the search for active substrates, optimum amount of phosphorus reagent and suitable catalysts for the reaction are summarized in Table 1. The progress of the reaction was monitored by gas-liquid chromatography (GLC) an...

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“…Therefore, the development of an effective novel aryl donor and the elucidation of its reactivity for the C–H arylation of benzofuran derivatives are required. Pentavalent organoantimony compounds such as triarylantimony diacetates [Ar 3 Sb(OAc) 2 ] and tetraphenylantimony acetate [Ph 4 Sb(OAc)] could be used as pseudo-halides for Pd-catalyzed C–C(Ar) bond formation in Heck- [ 30 , 31 , 32 ], Stille- [ 33 ], Hiyama- [ 34 ], Suzuki- [ 35 , 36 ] and Sonogashira-type reactions [ 37 ]. We also recently reported that triarylantimony difluorides (Ar 3 SbF 2 ) serve as an arylating reagent for the Pd-catalyzed β-selective C–H arylation of thiophenes [ 38 ].…”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed C–H Arylation of Benzofurans with Triarylantimony Difluorides for the Synthesis of 2-Arylbenzofurans

Kitamura¹,

Murata²,

Iwai³

et al. 2020

Molecules

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Pd-catalyzed regioselective C–H arylation is a useful tool for the chemical modification of aromatic heterocycles and 2-arylbenzofuran derivatives are of interest as biologically active substances. Herein, the reaction of triarylantimony difluorides with benzofurans under aerobic conditions in 1,2-DCE, using 5 mol% Pd (OAc)2 and 2 eq. of CuCl2 at 80 °C, produced a variety of 2-arylbenzofurans in moderate-to-high yields. The reaction is sensitive to the electronic nature of the substituents on the benzene ring of the triarylantimony difluorides: an electron-donating group showed higher reactivity than an electron-withdrawing group. Single crystal X-ray analysis of tri(p-methylphenyl) antimony difluoride revealed that the central antimony atom exhibits trigonal bipyramidal geometry.

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Tetraphenylantimony carboxylates in the cascade Pd-catalyzed C-phenylation reaction of methyl acrylate in the presence of peroxide

Cited by 31 publications

References 19 publications

Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

Pd‐Catalyzed β‐Selective C−H Arylation of Thiophenes with Triarylantimony Difluorides

Pd-Catalyzed P-Arylation of Triarylantimony Dicarboxylates with Dialkyl H-Phosphites without a Base: Synthesis of Arylphosphonates

Palladium-Catalyzed C–H Arylation of Benzofurans with Triarylantimony Difluorides for the Synthesis of 2-Arylbenzofurans

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