Palladium-catalyzed carbonylative cross-coupling of organoboranes with aryl iodides or benzyl halides in the presence of bis(acetylacetonato)zinc(II)

Wakita, Y.; Yasunaga, Tomohide; Akita, Masahiro; Kojima, Masayasu

doi:10.1016/0022-328x(86)80017-1

Cited by 65 publications

(18 citation statements)

References 9 publications

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“…An alternative process is transmetalation to an alkoxo-, hydroxo-, acetoxo-, or carbonylative coupling in the presence of Zn(acac) 2 [21]. Thus, the coupling reaction often proceeds under neutral conditions for organic electrophiles directly yielding such (oxo)palladium(II) species (9) via oxidative addition to a palladium(0) complex (path C).…”

Section: <>mentioning

confidence: 99%

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

Miyaura¹,

Suzuki²

1995

Chem. Rev.

12,328

6,287

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Until recently, organoboronic acids have been of limited use in organic synthesis due to their low reactivity for ionic reactions. During the past two decades; however, it has become increasingly clear that they are valuable reagents capable of undergoing many carbon-carbon bond formations in organic syntheses. In 1979, catalytic carbon-carbon bond formation, via transmetalation between organoboron compounds and palladium (II) halides, was found to proceed in the presence of a base. Historical PerspectivesAlthough organoboronic acids are highly advantageous as reagents in 1 laboratories and industries because they are largely unaffected by the presence of water, tolerate a broad range of functionalities, and yield nontoxic by-products, the boron-carbon bond is highly inert to ionic reactions. Transmetalation to other metals, especially to transition metals, is one promising process that enables the carbon-carbon bond formation by using organoboronic acids [1][2][3]. The interaction between 1-hexenylboronic acid and palladium(II) acetate was first demonstrated by Heck [4]. In situ preparation of (E)-or (Z)-1-alkenylpalladium(II) acetate via transmetalation was followed by its conjugate addition to ethyl acrylate (Scheme 1). Negishi found that boron-ate complexes such as lithium 1-alkynyltributylborate can participate in Pd-catalyzed cross-coupling [5,6]. Heck-type addition-elimination mechanism was proposed because other types of lithium tetraalkylborates, such as alkyl-, alkenyl-, and aryl derivatives, were unreactive. In spite of these previous observations, it was very difficult to use organoboron compounds to the palladium-catalyzed cross-coupling reaction; thus, an alternative and two-step procedure involving transmetalation of trialkylboranes to alkylmagnesium halides was developed by Murahashi [7].<>In 1976, we attempted a stoichiometric reaction between trialkylboranes and π-allylpalladium(II) chloride [8]. However, our first attempt failed because the reaction resulted in the exclusive formation of β-hydride elimination products. It was interesting that trialkylboranes readily alkylate π-allylpalladium(II) chloride without the assistance of a base immediately precipitating palladium black; however, a major process was quarternization of the boron atom with a negatively charged base enhances the nucleophilicity of the organic group on the boron atom for alkylation of R-Pd-X (6). 4Although there is no direct evidence for analogous hydroxyboronate anions, RB(OH) 3 -(7), which exists in alkaline solution in equilibrium with a free organoboronic acid, could similarly alkylate R-Pd-X (6) (path A). The transmetalation to 1 decreasing in the order of Cl > Br > I is the reverse of the oxidative addition of organic halides to palladium(0) complexes and is highly dependent on the counter cation of the added bases.<>An alternative process is transmetalation to an alkoxo-, hydroxo-, acetoxo-, or (acetylacetoxo)palladium(II) complex (9)

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Section: <>mentioning

confidence: 99%

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

Miyaura¹,

Suzuki²

1995

Chem. Rev.

12,328

6,287

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“…The general catalytic cycle for this carbonylative coupling reaction is analogous to the direct coupling except that carbon monoxide insertion takes place after the oxidative addition step and prior to the transmetallation step (Scheme Among a variety of organometallics for this purpose, organoboron compounds were first used by Kojima for the synthesis of alkyl aryl ketones [167]. The action of Zn(acac), in this reaction (Scheme 2-61) is ascribed to the formation of a RCOPdII(acac) species which undergoes transmetallation without assistance of bases (Scheme 2-20).…”

Section: Carbonylative Couplingmentioning

confidence: 99%

Cross‐Coupling Reactions of Organoboron Compounds with Organic Halides

Suzuki

1998

Metal‐Catalyzed Cross‐Coupling Reactions

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“…26,27 As significant as Suzuki chemistry has become, the true catalyst for its use was a derivative reaction first reported by Miyaura, which provided a straightforward route to the requisite arylboronic ester (and thus acid) starting materials (Scheme 6). 28 The new boronic acid chemistry was soon extended to include the coupling of a variety of aryl halides triflates with pinacol diboron and related reagents.…”

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confidence: 99%

Isotope incorporation via organoboranes

Kabalka

2007

Labelled Comp Radiopharmac

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Organoboranes can be used as precursors to a wide variety of functionally substituted, isotopically labeled compounds. Straightforward boron-based methods for incorporating short-lived and stable isotopes of carbon, nitrogen, oxygen, and the halogens have been developed over a period of 20 years. Application of these methods to biology, agriculture, and medicine has been slowed by the limited availability of boronated precursors containing functional groups appropriate to those fields. The situation has changed markedly with the advent of metal catalyzed boron-based reactions, which now produce a variety of important boronated materials readily available in the laboratory and from commercial sources. This is especially important in the medical and pharmaceutical communities where short-lived isotopes of carbon, nitrogen, and the halogens are demonstrating great value in positron and single photon emission tomographic procedures.

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Palladium-catalyzed carbonylative cross-coupling of organoboranes with aryl iodides or benzyl halides in the presence of bis(acetylacetonato)zinc(II)

Cited by 65 publications

References 9 publications

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds

Cross‐Coupling Reactions of Organoboron Compounds with Organic Halides

Isotope incorporation via organoboranes

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