Catalytic Addition of C – H Bonds to C – C Multiple Bonds

Kakiuchi, Fumitoshi

doi:10.1007/3418_2007_064

Cited by 67 publications

(2 citation statements)

References 108 publications

(122 reference statements)

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“…[1] Particularly, transitionmetal-catalyzed additions of arenes onto CÀC multiple bonds, namely, hydroarylation reactions, have received considerable attention as an ecologically and economically friendly approach to the direct functionalization [2] of aromatic C À H bonds. Consequently, a number of valuable protocols for intermolecular hydroarylation reactions of alkenes, alkynes, and allenes have been developed, [3] with ruthenium-catalyzed [4] directed [5] C À H bond functionalization among the most powerful strategies. [6,7] The chemistry of highly strained methylenecyclopropanes [8] continues to be fascinating because their enhanced reactivities allow fundamental concepts in organic chemistry to be probed and enable the development of novel synthetic methodologies.…”

Section: Introductionmentioning

confidence: 99%

“…Abstract: Intermolecular hydroarylation reactions of highly strained methylenecyclopropanes 2-phenylmethylenecyclopropane (1), 2,2-diphenylmethylenecyclopropane (2), methylenespiropentane (3), bicyclopropylidene (4), (dicyclopropylmethylene)cyclopropane (5), and benzhydrylidenecyclopropane (6) through C À H bond functionalization of 2-phenylpyridine (7 a) and other arenes with directing groups were studied. The reaction was very sensitive to the substitution on the methylenecyclopropanes.…”

Section: Introductionmentioning

confidence: 99%

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Ruthenium‐Catalyzed Hydroarylation of Methylenecyclopropanes through CH Bond Cleavage: Scope and Mechanism

Ackermann

Kozhushkov

Yufit

2012

Chemistry A European J

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Intermolecular hydroarylation reactions of highly strained methylenecyclopropanes 2-phenylmethylenecyclopropane (1), 2,2-diphenylmethylenecyclopropane (2), methylenespiropentane (3), bicyclopropylidene (4), (dicyclopropylmethylene)cyclopropane (5), and benzhydrylidenecyclopropane (6) through C-H bond functionalization of 2-phenylpyridine (7 a) and other arenes with directing groups were studied. The reaction was very sensitive to the substitution on the methylenecyclopropanes. Although these transformations involved (cyclopropylcarbinyl)-metal intermediates, substrates 1 and 4 furnished anti-Markovnikov hydroarylation products with complete conservation of all cyclopropane rings in 11-93 % yield, whereas starting materials 3 and 5 were inert toward hydroarylation. Methylenecyclopropane 6 formed the products of formal hydroarylation reactions of the longest distal C-C bond in the methylenecyclopropane moiety in high yield, and hydrocarbon 2 afforded mixtures of hydroarylated products in low yields with a predominance of compounds that retained the cyclopropane unit. As byproducts, Diels-Alder cycloadducts and self-reorganization products were obtained in several cases from substrates 1-3 and 5. The structures of the most important new products have been unambiguously determined by X-ray diffraction analyses. On the basis of the results of hydroarylation experiments with isotopically labeled 7 a-[D(5)], a plausible mechanistic rationale and a catalytic cycle for these unusual ruthenium-catalyzed hydroarylation reactions have been proposed. Arene-tethered ruthenium-phosphane complex 53, either isolated from the reaction mixture or independently prepared, did not show any catalytic activity.

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