Catalytic Carbonylation Reactions of Benzyne Derivatives

Chatani, Naoto; Kamitani, Akihito; Oshita, Masayuki; Fukumoto, Yoshiya; Murai, Shinji

doi:10.1021/ja011923c

Cited by 83 publications

(46 citation statements)

References 12 publications

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“…Similar products are obtained by the palladiumcatalyzed carbonylative coupling of allyl acetate with benzynes [20].…”

mentioning

confidence: 59%

Carbonylative Heck Reactions

Beller

2013

Transition Metal Catalyzed Carbonylation Reactions

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The ''Carbonylative Heck Reaction'' is not the same as those that were traditionally called ''Heck carbonylations''. Heck carbonylations normally include alkoxycarbonylation, aminocarbonylation and hydroxycarbonylation, while a carbonylative Heck reaction is more related to a Heck reaction. In the late 1960s, Richard Heck developed several coupling reactions of arylmercury compounds in the presence of either stoichiometric or catalytic amounts of palladium salts [1][2][3][4][5][6][7]. Based on this work in 1972, he described a protocol for the coupling of iodobenzene with styrene, which today is known as the ''Heck reaction '' [8]. In contrast to this, the catalytic insertion of olefins into acylpalladium complexes is called a ''Carbonylative Heck reaction''. Here the acylpalladium complexes can either by CO insertion or by the oxidative addition of benzoyl precursors [9,10].The first palladium-catalyzed copolymerization of carbon monoxide (CO) with olefins was described in 1982 [11], and as a consequence, carbonylative coupling reactions with alkenes were reported soon after. Notably, it was Negishi and Miller who discovered the first two examples of intramolecular carbonylative Heck reactions of 1-iodopenta-1,4-dienes by applying stoichiometric amounts of palladium [12]. 5-Methylenecyclopent-2-enones as the products were produced in moderate yields (Scheme 7.1).However, using 1a-1e as substrates, no desired carbonylation products were detected, although the complete conversion of starting material occurred. Presumably, the polymerization of 1a-1e (Scheme 7.2) took place [13]. Negishi and Miller's group improved the methodology two years later [14]. In their new methodology, 1a-1e were applied as starting materials and the corresponding products were obtained in moderate to excellent yields using catalytic amounts of palladium salts in the presence of MeOH. A possible reaction mechanism was proposed, and ''CO-free'' carbonylative Heck reactions were realized. 2-Methylene-2,3-dihydro-inden-1-one 1g was produced from the corresponding acid chloride 1f in a 50 % yield under ''CO-free'' conditions. Negishi et al. continued their interest in this topic by synthesizing various quinones using o-iodoaryl cyclohexyl ketones as the starting materials [15]. In the presence of Pd(dba) 2 as a catalyst (5 mol %) and under CO pressure (41 bar), quinones were produced in good yields with 100 % regioselectivity (Scheme 7.3).

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“…Similar products are obtained by the palladiumcatalyzed carbonylative coupling of allyl acetate with benzynes [20].…”

mentioning

confidence: 59%

Carbonylative Heck Reactions

Beller

2013

Transition Metal Catalyzed Carbonylation Reactions

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“…Thus, when 3-methoxy-2-(trimethylsilyl)phenyl triflate (8) was used as the substituted benzyne precursor, tributyl(2-methoxyphenyl)stannane (10) was exclusively formed in 78% isolated yield. The corresponding deuterated stannane 11 could also be exclusively formed with Bu 3 SnD.…”

Section: Scheme 2 Hydrostannation Of Benzyne Generated From Anthranilmentioning

confidence: 99%

“…4 For example, studies of palladium-catalysed aryne trimerisation, 5 annulation 6 and co-cyclisations of arynes with alkynes, 7 have opened up many new possibilities in synthesis. 8 Transition-metal-catalysed insertion reactions with transient aryne intermediates were first reported by Yoshida and co-workers. In their pioneering studies, efficient palladium-mediated carbostannylations were achieved under mild conditions with a range of organostannanes. 9…”

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confidence: 98%

Catalyst-Free Regioselective Hydrostannation of Arynes

Spiteri¹,

Burnley²,

Moses³

2011

Synlett

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We report the first regioselective hydrostannation of an aryne. Excellent yields were achieved under mild room temperature conditions without the use of additives or catalysts. Preliminary investigations into the effects of substituents have been conducted, revealing impressive levels of regiochemical control. The method also offers a unique route to access 1,2-deuterated arylstannanes demonstrating the power and potential of this chemistry.Arynes are versatile reactive intermediates that participate in many reactions including cycloadditions, 1 nucleophilic additions 2 and electrophile trappings. 3 Transition-metal complex catalysed transformations of arynes have emerged as attractive routes to substituted arenes that are not easily accessible by conventional methods. 4 For example, studies of palladium-catalysed aryne trimerisation, 5 annulation 6 and co-cyclisations of arynes with alkynes, 7 have opened up many new possibilities in synthesis. 8 Transition-metal-catalysed insertion reactions with transient aryne intermediates were first reported by Yoshida and co-workers. In their pioneering studies, efficient palladium-mediated carbostannylations were achieved under mild conditions with a range of organostannanes. 9

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“…Recently, transition metal-catalyzed reactions involving arynes, which are generated by fluoride-induced elimination of Kobayashi's silylaryl triflate under mild conditions [5], have been well documented [6][7][8][9][10][11][12][13][14][15][16][17]. Since Guitián and co-workers [6] first reported Pd(0)-catalyzed cyclotrimerization of arynes to generate triphenylenes in 1998 (Scheme 1), a variety of important triphenylene derivatives, which demonstrated potent applications in organic materials, have been prepared under similar reaction conditions [18][19][20][21][22][23][24][25].…”

Section: Introductionmentioning

confidence: 99%