Efficient Cross-Coupling of Functionalized Arylzinc Halides Catalyzed by a Nickel Chloride−Diethyl Phosphite System

Gavryushin, Andrei; Kofink, Christiane; Manolikakes, Georg; Knöchel, Paul

doi:10.1021/ol051615+

Cited by 64 publications

(26 citation statements)

References 29 publications

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“…[14] Common methods for the introduction of late transition and p-block metals often utilize the abovementioned lithiated or magnesiated derivatives in metal-exchange reactions. [13,15,16] Notably, there have been various reports on the allylation of (iso)quinolines with allylic reagents of boron, [17] tin, [17d, 18] silicon, [12d, 17d, 18a, 19] indium, [18e, 20] and magnesium. [21] As was found for the activation of pyridine itself, these transformations mostly require N-acylation prior to functionalization, and, with some exceptions, give the desired allylated derivatives in yields lower than 80 %.…”

Section: Introductionmentioning

confidence: 99%

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Jochmann

Leich

Spaniol

et al. 2011

Chemistry A European J

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A facile and general synthetic pathway for the production of dearomatized, allylated, and C-H bond activated pyridine derivatives is presented. Reaction of the corresponding derivative with the previously reported reagent bis(allyl)calcium, [Ca(C(3)H(5))(2)] (1), cleanly affords the product in high yield. The range of N-heterocyclic compounds studied comprised 2-picoline (2), 4-picoline (3), 2,6-lutidine (4), 4-tert-butylpyridine (5), 2,2'-bipyridine (6), acridine (7), quinoline (8), and isoquinoline (9). Depending on the substitution pattern of the pyridine derivative, either carbometalation or C-H bond activation products are obtained. In the absence of methyl groups ortho or para to the nitrogen atom, carbometalation leads to dearomatized products. C(sp(3))-H bond activation occurs at ortho and para situated methyl groups. Steric shielding of the 4-position in pyridine yields the ring-metalated product through C(sp(2))-H bond activation instead. The isolated compounds [Ca(2-CH(2)-C(5)H(4)N)(2)(THF)] (2b⋅(THF)), [Ca(4-CH(2)-C(5)H(4)N)(2)(THF)(2)] (3b⋅(THF)(2)), [Ca(2-CH(2)-C(5)H(3)N-6-CH(3))(2)(THF)(n)] (4b⋅(THF)(n); n=0, 0.75), [Ca{2-C(5)H(3)N-4-C(CH(3))(3)}(2)(THF)(2)] (5c⋅(THF)(2)), [Ca{4,4'-(C(3)H(5))(2)-(C(10)H(8)N(2))}(THF)] (6a⋅(THF)), [Ca(NC(13) H(9)-9-C(3)H(5))(2)(THF)] (7a⋅(THF)), [Ca(4-C(3) H(5)-C(9) H(7)N)(2)(THF)] (8b⋅(THF)), and [Ca(1-C(3)H(5)-C(9)H(7) N)(2)(THF)(3)] (9a⋅(THF)(3)) have been characterized by NMR spectroscopy and metal analysis. 9a⋅(THF)(4) and 4b⋅(THF)(3) were additionally characterized in the solid state by X-ray diffraction experiments. 4b⋅(THF)(3) shows an aza-allyl coordination mode in the solid state. Based on the results, mechanistic aspects are discussed in the context of previous findings.

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Section: Introductionmentioning

confidence: 99%

Calcium‐Mediated Dearomatization, CH Bond Activation, and Allylation of Alkylated and Benzannulated Pyridine Derivatives

Jochmann

Leich

Spaniol

et al. 2011

Chemistry A European J

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“…As illustrated with the formation of 244, the combination of NiCl 2 with diethyl phosphite and N,N-dimethylaminopyridine (DMAP) as ligands can be used to carry out the cross-coupling reaction of aryl-and heteroarylzinc bromides with aryl bromides and tosylates at rt in a THF/N-ethylpyrrolidone (NEP) mixture (Scheme 4.54) [197]. Aryl chlorides are also suitable partners, but extended reaction times are required.…”

Section: Nickel-catalyzed Cross-coupling Reactionsmentioning

confidence: 99%

Carbon–Carbon Bond Forming Reactions Mediated by Organozinc Reagents

Chemla

Ferreira

Jackowski

et al. 2013

Metal‐Catalyzed Cross‐Coupling Reactions and More

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“…453 The nickel(II) chloride-diethyl phosphite system has been used as catalyst in cross-coupling reactions or organozincs, such as the coupling of (1-methylpyrrol-2-yl)zinc bromide with 3-bromopyridine. 454 Iron trichloride has also been used as catalyst in the cross-coupling reaction of some heteroarylzincs with alkyl halides, the reaction occurring probably through radical intermediates. Thus, N-methylated 2-indolylzinc derivative 253, bearing a nontransferable (trimethylsilyl)methyl group, was generated upon treatment of the organozinc reagent 252 with [(trimethylsilyl)methyl]magnesium chloride, and reacted with cyclohexylchloride in the presence of catalytic amount of iron trichloride to give the corresponding 2-substituted indole 254 (Scheme 75).…”

Section: Aromatic Five-membered Ringsmentioning

confidence: 99%