Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes

Miyaura, Norio; Yamada, Kuriko; Suginome, Hiroshi; Suzuki, Akira

doi:10.1021/ja00290a037

Cited by 509 publications

(188 citation statements)

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“…The 9-decyn-1-ol was converted to (E)-10-hydoxy-2-fluoro-1-decenyliodonium fluoride (9a) by the reaction with Et 3 N-5HF and p-iodotoluene difluoride (ITDF), electrochemically prepared from p-iodotoluene [11], and the resulting 9a, without isolation, was converted to 9b by the reaction with CuI and KI [11,15,16]. The cross-coupling reaction of (E)-(1-butenyl)diisopropoxyborane with 9b using Pd(PPh 3 ) 4 as a catalyst was sluggish and a significant amount of a head-to-tail coupling by-product was formed as well as a normal coupling product [17]. This problem could be overcome by using Pd(OAc) 2 -BINAP as catalyst and the desired 7 could be obtained in 57% yield from 9b after acetylation of the hydoxyl group (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Stereoselective synthesis of insect sex pheromone analogs having a fluorine atom on their double bonds

Guan

Yoshida

Ota

et al. 2005

Journal of Fluorine Chemistry

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Section: Resultsmentioning

confidence: 99%

Stereoselective synthesis of insect sex pheromone analogs having a fluorine atom on their double bonds

Guan

Yoshida

Ota

et al. 2005

Journal of Fluorine Chemistry

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“…Recently some research groups, especially Fu's group 19 and Buchwald's group 9,20 have reported very efficient methods for aryl chloride reaction. For example, Fu and his co-workers 19 have observed that the use of [Pd 2 (dba) 3 ]/P( t Bu) 3 (dba: dibenzylideneacetone) as a catalyst and ligand for a wide range of aryl and vinyl halides, including chlorides, undergo the Suzuki cross-coupling with arylboronic acids in very good yield, typically at room temperature. Furthermore, these catalysts display novel reactivity patterns, such as the selective coupling by [Pd 2 (dba) 3 ]/ PCy 3 /KF of a sterically hindered aromatic chloride.…”

Section: ç Coupling With Aromatic Chloridesmentioning

confidence: 99%

“…Although organometallic reagents with 1-alkenyl, 1-alkynyl, and aryl groups were successfully used for the coupling reactions, those with alkyl groups having sp 3 carbons containing ¢-hydrogens were severely limited due to the competitive side reactions. In 19711972 Kochi, Kumada, and Corriu reported independently that the reaction of alkyl Grignard reagents with alkenyl or aryl halides are markedly catalyzed by Fe(III) or Ni(II) complexes, and then Negishi demonstrated the synthetic utility of alkylzinc compounds by use of palladium catalyst.…”

Section: ç Coupling Of B-alkyl-boranes With Alkenyl or Aryl Halidesmentioning

confidence: 99%

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Cross-coupling Reactions of Organoboranes: An Easy Method for C–C Bonding

Suzuki¹,

Yamamoto²

2011

Chemistry Letters

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147

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The palladium-catalyzed cross-coupling reaction between different types of organoboron compounds and various organic halides or triflates in the presence of base provides a powerful and general methodology for the formation of carboncarbon bonds. The Csp 2 B compounds (such as aryl-and 1-alkenylboron derivatives) and Csp 3 B compounds (alkylboron compounds) readily cross-couple with organic electrophiles to give coupled products selectively in high yields. Recently, the CspB compounds (1-alkynylboron derivatives) have been also observed to react with organic electrophiles to produce expected cross-coupled products. The overview of some of such coupling reactions is discussed here in this article. Ç IntroductionCarboncarbon bond formation reactions are important processes in chemistry, because they provide key steps in building complex, bioactive molecules developed as pharmaceuticals and agrochemicals. They are also vital in developing a new generation of ingeniously designed organic materials with novel electronic, optical, or mechanical properties, likely to play a significant role in the burgeoning area of nanotechnology.During the past 40 years, most important carboncarbon bond-forming methodologies have involved using transition metals to mediate the reactions in a controlled and selective manner. The palladium-catalyzed cross-coupling reaction between different types of organoboron compounds and various organic electrophiles including halides or triflates in the presence of base provides a powerful and general methodology for the formation of carboncarbon bonds. Here, some representatives of such reactions are shown in Scheme 1. Numbers in parentheses indicate the years first reported by our group.As one defect of the reaction, one would point out the use of bases. However, the difficulty could be overcome by using suitable solvent systems and adequate bases. Consequently, these coupling reactions have been actively utilized not only in academic laboratories but also in industrial processes. In this paper, three topics, routes to conjugated alkadienes, application to biaryls, and B-alkyl-borane coupling will be discussed. In addition, recent topics will be introduced.Such coupling reactions offer several advantages: (1) Ready availability of reactants. Cross-coupling reactions between vinylic boranes and vinylic halides were not reported to proceed smoothly in the presence of only palladium catalysts. During the initial stage of our exploration, we postulated that a drawback of the coupling is caused by the following aspects of the mechanism. The common mechanism of transition-metal-catalyzed coupling reactions of organometallic compounds with organic halides involves sequential (a) oxidative addition, (b) transmetalation, and (c) reductive elimination.1 It appeared that one of the major reasons that 1-alkenylboranes cannot react with 1-alkenyl halides is step (b). The transmetalation process between RMX (M = transition metal, X = halogen) and organoboranes does not occur readily because of the wea...

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“…La préparation à grande échelle de composés pharmaceutiques tels que le PDE472 (Novartis), un inhibiteur de la phosphodiestérase ; le 2-chloro(-pyridin-2-yl) pyrimidine, un intermédiaire-clé dans la synthèse d'inhibiteur sélectif du PDE-V (phosphodiestérase), un puissant vasodilatateur (Johnson & Johnson), utilise cette méthodologie. [11,12]. Ces auteurs ont également décrit en 1981 la première méthode générale de synthèse de dérivés biaryliques, par couplage croisé entre un dérivé arylhalogénure et un composé arylboronique en présence de (tétrakis)triphénylphosphine palladium : Pd(PPh 3 ) 4 .…”

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Le palladium, un catalyseur magique au service des chimistes

Genêt

2010

Med Sci (Paris)

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Le palladium, un catalyseur magique au service des chimistes Jean-Pierre GenetLe palladium, découvert en 1903 par Wollatson, est un métal rare. Le nom qui lui fut attribué l'année suivant sa découverte dérive de l'astéroïde Pallas, Palladium en grec. Cette appellation fait référence à la déesse mythologique de la sagesse et du savoir. Le palladium est utilisé dans l'industrie automobile (pots catalytiques), dans la fabrication des composants électroniques pour les portables, les ordinateurs et l'électronique. L'activité du palladium et de ses dérivés organométalliques synthétiquement utiles est favorisée principalement aux états d'oxydation 0 et 2. La chimie du palladium est très « chimiosélective » et a magistralement complété la traditionnelle chimie des Grignards 1 et des organolithiens 2 . Le développement des réactions catalytiques utilisant le palladium en synthèse organique a été beaucoup moins rapide que celui de la chimie organométallique classique.1 Du nom de Victor Grignard, prix Nobel à 41 ans, qui fait partie des grands chimistes français qui ont laissé leur nom dans l'histoire. C'est en effet le seul qui figure dans tous les ouvrages de chimie organique, du plus simple au plus complexe, pour avoir mis au point la préparation des organomagnésiens, une classe de molécules particulièrement utilisées en synthèse organique. 2 Les organomagnésiens et les organolithiens font partie de la famille des organométalliques définis comme des composés dans lesquels il existe une liaison métal-carbone.

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Novel and convenient method for the stereo- and regiospecific synthesis of conjugated alkadienes and alkenynes via the palladium-catalyzed cross-coupling reaction of 1-alkenylboranes with bromoalkenes and bromoalkynes

Cited by 509 publications

References 9 publications

Stereoselective synthesis of insect sex pheromone analogs having a fluorine atom on their double bonds

Stereoselective synthesis of insect sex pheromone analogs having a fluorine atom on their double bonds

Cross-coupling Reactions of Organoboranes: An Easy Method for C–C Bonding

Le palladium, un catalyseur magique au service des chimistes

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