Cobalt-Catalyzed Heck-Type Reaction of Alkyl Halides with Styrenes

Ikeda, Yōnosuke; Nakamura, Tomoaki; Yorimitsu, Hideki; Oshima, Koichiro

doi:10.1021/ja026296l

Cited by 256 publications

(76 citation statements)

References 12 publications

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“…This system can allow the introduction of a carbon moiety carrying an ester group (run 9). Under the same conditions, CH 2 ¼ CHMgBr, PhB(OH) 2 , and PhC ¼ CSn(n-Bu) 3 were ineffective.…”

Section: ð1þmentioning

confidence: 97%

“…Competitive reactions of a mixture of primary, secondary, and tertiary alkyl bromides showed that the reactivities of the halides increase in the order primary < secondary < tertiary. A possible reaction pathway involving single electron transfer from a nickelate complex to alkyl halides is proposed.Keywords: alkyl halides; butadiene; C À C bond formation; cross-coupling; Grignard reagents; multicomponent reactions; nickelThe transition metal catalyzed coupling reaction of organic halides with organometallic reagents or alkenes has been extensively studied and employed in wide areas of organic synthesis.[1] These types of reactions are initiated generally by the oxidative addition of halides to low-valent metals such as Ni 0 and Pd 0 and the scope of the halides as substrates has been limited to aryl, vinyl, allyl, and benzyl halides, [2,3] partly, due to the slow oxidative addition of alkyl halides to metal complexes. Facile b-elimination from the alkylmetal intermediates also restricted the application of alkyl halides.…”

mentioning

confidence: 99%

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Nickel‐Catalyzed Regioselective Three Component Coupling Reaction of Alkyl Halides, Butadienes, and Ar‐M (M=MgX, ZnX)

et al. 2004

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A new method for the regioselective three component cross-coupling reaction of alkyl halides, 1,3-butadienes, and aryl-Grignard reagents has been developed by the use of a nickel catalyst. This reaction proceeds efficiently at 25 8C using (dppf) NiCl 2 as a catalyst. Alkyl chlorides, bromides, and iodides can be used as suitable alkylating reagents. The reaction also proceeds when arylzinc halides are used instead of Grignard reagents. Competitive reactions of a mixture of primary, secondary, and tertiary alkyl bromides showed that the reactivities of the halides increase in the order primary < secondary < tertiary. A possible reaction pathway involving single electron transfer from a nickelate complex to alkyl halides is proposed.Keywords: alkyl halides; butadiene; C À C bond formation; cross-coupling; Grignard reagents; multicomponent reactions; nickelThe transition metal catalyzed coupling reaction of organic halides with organometallic reagents or alkenes has been extensively studied and employed in wide areas of organic synthesis.[1] These types of reactions are initiated generally by the oxidative addition of halides to low-valent metals such as Ni 0 and Pd 0 and the scope of the halides as substrates has been limited to aryl, vinyl, allyl, and benzyl halides, [2,3] partly, due to the slow oxidative addition of alkyl halides to metal complexes. Facile b-elimination from the alkylmetal intermediates also restricted the application of alkyl halides. In pursuit of finding novel uses for alkyl halides in transition metal catalyzed reaction, we have recently developed a new type of Ni [4] or Pd [5] catalyzed crosscoupling reaction of alkyl halides with Grignard reagents in the presence of 1,3-butadiene where bisallylmetalate complexes play important roles as active catalytic species. When we examined this reaction using [(dppf)NiCl 2 ], we found an unprecedented three component coupling reaction of alkyl halides, 1,3-butadienes, and arylmagnesium or arylzinc reagents [Eq. (1)]. ð1ÞFor example, into a mixture of isopropyl bromide (1.2 mmol), 2,3-dimethyl-1,3-butadiene (1 mmol), and [(dppf)NiCl 2 ] (0.08 mmol) was added a THF solution of PhMgBr (1.5 mmol, 1.5 mL). The solution was stirred at 25 8C for 24 h. Usual work-up and NMR analysis of the crude mixture indicated the formation of a coupling product 4b (R ¼ i-Pr, R' ¼ Me, R'' ¼ H, Ar ¼ Ph) bearing isopropyl and phenyl groups at the terminal carbons of the 1,3-butadiene unit in 99% yield by NMR (E/Z ¼ 67/33) ( Table 1, run 2). The product was obtained in pure form in 91% yield by recycling preparative HPLC using CHCl 3 as an eluent. Neither regioisomers of 4b nor isopropylbenzene (direct coupling product of i-PrBr with PhMgBr) were formed. The elongation of reaction time did not lead to isomerization of the double bond of the product.

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“…This system can allow the introduction of a carbon moiety carrying an ester group (run 9). Under the same conditions, CH 2 ¼ CHMgBr, PhB(OH) 2 , and PhC ¼ CSn(n-Bu) 3 were ineffective.…”

Section: ð1þmentioning

confidence: 97%

mentioning

confidence: 99%

Nickel‐Catalyzed Regioselective Three Component Coupling Reaction of Alkyl Halides, Butadienes, and Ar‐M (M=MgX, ZnX)

et al. 2004

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“…Oshimas Gruppe entwickelte eine cobaltkatalysierte Variante, bei der sekundäre Alkylbromide mit Styrolderivaten gekuppelt werden. [49] Hierzu sind der Einsatz von 1,6-Bis(diphenylphosphanyl)hexan (dpph) als Ligand sowie ein Überschuss an Alkylhalogenid (1.5 ¾quiv) erforderlich. Die Zugabe von Trimethylsilylmethylmagnesiumbromid ist notwendig, jedoch wird dieses nicht ins Produkt eingebaut (Schema 26).…”

Section: Heck-reaktionen Mit Organometallnucleophilenunclassified

Sekundäre Alkylhalogenide in übergangsmetallkatalysierten Kreuzkupplungen

2009

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Sekundär, aber nicht zweitrangig: In den vergangenen fünf Jahren hat die Verwendung von sekundären Alkylhalogeniden in übergangsmetallkatalysierten Kreuzkupplungen erheblich zugenommen. Hier werden ausgewählte Beispiele für solche Prozesse unter Berücksichtigung von mechanistischen und stereochemischen Aspekten betrachtet.magnified imageEs wurde viel Kraft in die Entwicklung von metallkatalysierten Kreuzkupplungen mit Alkylhalogeniden als elektrophile Reaktionspartner investiert. Während schon heute zahlreiche primäre Alkylhalogenide wirksam in Kreuzkupplungen verwendet werden können, stehen Umsetzungen mit sekundären Alkylhalogeniden gerade erst am Anfang. Hier werden ausgewählte Kreuzkupplungen vorgestellt, in denen sekundäre Alkylhalogenide als Elektrophile wirken. Dabei wird den verwendeten Übergangsmetallen, den Reaktionsmechanismen und dem stereochemischen Verlauf besondere Beachtung geschenkt.

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“…236 Articles describing, or of relevance to, catalytic reactions of group 9 metals that have not been mentioned above include the detection by in situ IR spectroscopy of the 'missing link' [HRh(CO) 4 ] for the first time, 4 the use of parahydrogen for the detection of rhodium and iridium species present in very low concentration during hydroformylation of alkenes, 237,238 the nature and roles of catalytic promoters in late metal carbonylation reactions, 239 and a DFT study of cobalt-mediated alkene polymerisation which detects an inverse isotope effect due to a β-agostic interaction in the resting state of the catalyst [Cp*Co(Et)(P(OMe) 3 )] ϩ . 240 Important alkyl coupling reactions have also been investigated including cobalt-catalysed Heck-type reactions between alkyl halides and styrene 241 and alkyl halides and allylic Grignard reagents. 242 The direct observation and mechanism of aldehyde insertion into rhodium() aryl and alkoxide complexes has also been reported and intermediates characterised.…”

Section: Cobalt Rhodium Iridiummentioning

confidence: 99%