Intermolecular chemistry of a dialkylcarbene: Adamantanylidene

Moss, Robert A.; Chang, Ming Jing

doi:10.1016/s0040-4039(01)82010-4

Cited by 38 publications

(24 citation statements)

References 14 publications

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“…[20][21][22] Therefore it is necessary to identify a clear-cut photolytic experimental results. Most cases 14,15,23,24 show there are different electronic spin-state in accordance with producing from diazirine derivatives or diazo derivatives as shown in Scheme 6.…”

mentioning

confidence: 86%

“…11 Generally, alkylcarbenes give ylide intermediates, 7 in their trapping compounds as acetonitrile or pyridine. [12][13][14][15][16][17] Although many alkylketocarbene reactions with acetonitrile or pyridine quenchers have been studied, the ylide intermediates involving arylketocarbene with acetonitrile or pyridine have not yet reported.…”

Section: Introductionmentioning

confidence: 99%

“…[8][9][10][11][12][13][14][15][16][17][18][19] Generally it is well known that photolysis of alkyl carbomethoxy carbene gives a product of triplet sensitization. Triplet sensitization lowers the yield of the product abstracted from singlet carbene as well as the yield of the product of C-H insertion.…”

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confidence: 99%

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Interconversion of Electronic Spin State of p-Substituted Arylketocarbene Reactions

2004

Bulletin of the Korean Chemical Society

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Rate constants for photolytic reactions of p-substituted 2-diazopropiophenones were determined in acetonitrile. The reactions show a comparatively low value of activation energy and activation enthalpy to alkylcarbenes or other arylcarbenes. The transition state corresponds to the step of a new carbonyl bond formation. The high negative ρ-values are shown in Hammett plots. The kinetics results and EPR spectrum are in accord with a phenomenon that occurs in interconversion between singlet and triplet carbenes.

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confidence: 86%

Section: Introductionmentioning

confidence: 99%

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Interconversion of Electronic Spin State of p-Substituted Arylketocarbene Reactions

2004

Bulletin of the Korean Chemical Society

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“…[99][100][101] Its precursor, 2-aziadamantane (8), [102] has been widely studied. [103,104] Believed to have a singlet GS, [105] carbene 11 does not readily undergo a 1,2-H shift to form the strained anti-Bredt compound singlet adamantene (12) (Scheme 5). [106] Thus, other rearrangements of carbene 11 can flourish.…”

Section: 3-ch Insertionmentioning

confidence: 99%

Constrained Carbenes

Rosenberg

Brinker

2006

Eur J Org Chem

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Carbenes traditionally have been used for cyclopropane synthesis but little else, since their reactions are difficult to control. However, the burgeoning discipline of supramolecular carbene chemistry—reactions in which highly reactive, divalent carbon intermediates are generated within the confines of host compounds—is making steady progress towards solving this problem. Various carbenes generated within cyclodextrins, hemicarcerands, and zeolites demonstrate increased selectivities and lifetimes since their usual decay pathways are blocked. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

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“…14 Adamantane diazirine is an especially convenient precursor for carbene investigation since it is stable and easy to handle. 15 Moreover, the formed adamantylidene can only undergo one type of intramolecular reaction: insertion into the γ-CH bond. [16][17][18][19] A rigid adamantane backbone and its inability to form anti-Bredt olefins results in a somewhat longer lifetime of the generated carbene, rendering it appropriate for the study of reactivity in intermolecular reactions.…”

Section: Introductionmentioning

confidence: 99%