Preparation of triarylantimony(V) diacetates and palladium-catalyzed cross-coupling and carbonylative cross-coupling of triarylantimony(V) diacetates and dichlorides with organostannanes

Kang, Suk‐Ku; Ryu, Hyung-Chul; Lee, Sang‐Woo

doi:10.1016/s0022-328x(00)00386-7

Cited by 42 publications

(13 citation statements)

References 31 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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“…[14][15][16][17][18][19][20][21] The organoantimony(III) [Sb(III)] compounds are relatively stable and can be prepared easily compared to organoantimony(V) and hypervalent antimony compounds. The facile access of Sb(III) compounds stimulated us to employ them as practical organic reagents.…”

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confidence: 99%

“…12,13) One useful application of these transmetallating agents is carbonylative cross-coupling reaction which leads to the formation of unsymmetrical ketones in one-pot operation from an appropriate transmetallating agent and organic halides under carbon monoxide (CO) atmosphere. [14][15][16][17][18][19][20][21] The organoantimony(III) [Sb(III)] compounds are relatively stable and can be prepared easily compared to organoantimony(V) and hypervalent antimony compounds. The facile access of Sb(III) compounds stimulated us to employ them as practical organic reagents.…”

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confidence: 99%

Carbonylative Cross-Coupling Reaction of Ethynylstibane with Aryl Iodides

Kakusawa

Kurita

2006

CHEMICAL & PHARMACEUTICAL BULLETIN

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Recent remarkable development of novel transmetallating agents for cross-coupling reactions has been fascinating to many synthetic chemists because of its high reliability and wide applicability for C-C, C-O and C-N bond forming reaction.1,2) Especially, investigations on novel coupling agents involving typical heavier elements such as In, 3,4) Si, 5-7) Bi, 8,9) and Ge 10,11) attract much attention not only of heteroatom chemists, but also of synthetic chemists. These transmetallating agents can easily be activated and coupled with various organic halides under mild condition, based on a hypervalent strategy.12,13) One useful application of these transmetallating agents is carbonylative cross-coupling reaction which leads to the formation of unsymmetrical ketones in one-pot operation from an appropriate transmetallating agent and organic halides under carbon monoxide (CO) atmosphere. [14][15][16][17][18][19][20][21] The organoantimony(III) [Sb(III)] compounds are relatively stable and can be prepared easily compared to organoantimony(V) and hypervalent antimony compounds. The facile access of Sb(III) compounds stimulated us to employ them as practical organic reagents. We have recently explored the palladium-catalyzed cross-coupling reaction of Sb(III) compounds with organic halides and their versatile applicability, e.g. ethynylstibanes (1) were coupled with acyl chlorides, vinyl iodides and aryl iodides to give ethynylketones, 1,3-enynes, and arylacetylens, respectively. 22,23) We also demonstrated that these reactions were accelerated with microwave irradiation. 24) A mild and efficient Sb(III)-mediated cross-coupling reaction was also achieved with ethynyland ary-1,5-azastibocienes bearing an intramolecular N … Sb non-bonding interaction. 25,26) As an extension of the versatility of Sb(III) compounds as a transmetallating agent, we investigated the cross-coupling reaction of ethynylstibanes with aryl iodides under CO atmosphere. In the present reaction, the yield of the carbonylated coupling products is sensitive to the nature of the Pd catalyst, and superior results were obtained by using a monodentate phosphine-ligated Pd catalyst. It also appeared that a variety of unsymmetrical ethynyl ketones could be synthesized in excellent yield under high pressure condition (CO, 20 atm) even in the reactions with electron-deficient aryl iodides which usually gave inferior results due to their tendency to undergo decarbonylation. Results and DiscussionPd-Catalyzed Carbonylative Cross-Coupling Reaction of Ethynylstibane with Aryl Iodides under CO Atmosphere In order to optimize the reaction conditions, we initially attempted the reaction of ethynyldiphenylstibane (1) and iodobezene (2a) under atmospheric CO pressure using a variety of solvents in the presence of 5 mol% of various palladium (Pd) catalysts (Table 1). The reaction did not proceed in THF or benzene which was often employed for carbonylative cross-coupling with a variety of organometallic compounds.2,14-16,18,21) For direct cross-coupling reaction of 1 and...

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Preparation of triarylantimony(V) diacetates and palladium-catalyzed cross-coupling and carbonylative cross-coupling of triarylantimony(V) diacetates and dichlorides with organostannanes

Cited by 42 publications

References 31 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

Carbonylative Cross-Coupling Reaction of Ethynylstibane with Aryl Iodides

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