Reactive species: Ynols and ynamines

Chiang, Y.; Kresge, A. J.; Paine, Stuart W.; Popik, Vladimir V.

doi:10.1002/(sici)1099-1395(199606)9:6<361::aid-poc793>3.0.co;2-y

Cited by 22 publications

(9 citation statements)

References 33 publications

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“…15 This reaction can be induced by NIR light under two-photon excitation conditions 16 and proceeds smoothly in the solid state. 17 We have already employed this reaction for the generation of reactive triple bonds in ynols, 18 enediynes, 19 and dibenzocyclooctynes. 20 Irradiation of bis-cyclopropenone 1 (photo-DIBOD) results in the formation of the Sondheimer diyne 2 , which, in turn reacts with two azide-functionalized substrates to create a stable covalent cross-link (Scheme 1).…”

mentioning

confidence: 99%

Cyclopropenone-caged Sondheimer diyne (dibenzo[a,e]cyclooctadiyne): a photoactivatable linchpin for efficient SPAAC crosslinking

Sutton

Steet

et al. 2016

Chem. Commun.

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The first fully conjugated bis-cyclopropenone (photo-DIBOD), a derivative of dibenzo[a,e][8]annulene, has been synthesized. 350–420 nm irradiation of this robust compounds results in the efficient formation of dibenzo [a, e] cyclooctadiyne, an unstable, but useful SPAAC cross-linking reagent. Since photo-DIBO doesn’t react with organic azides, this method allows for the spatiotemporal control of the ligation of two azide-tagged substrates.

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mentioning

confidence: 99%

Cyclopropenone-caged Sondheimer diyne (dibenzo[a,e]cyclooctadiyne): a photoactivatable linchpin for efficient SPAAC crosslinking

Sutton

Steet

et al. 2016

Chem. Commun.

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“…In 2012, Rabasso published a [2,3]-sigmatropic rearrangement of N -alkynyl amides [118]. The following year, 2013, during their investigations into the selective reduction of amino-allenephosphonates, Rabasso expanded the scope of their [2,3]-sigmatropic rearrangement to include N -alkynyl indole (Scheme 75) [119]. The researchers found that compound 279 , underwent a [2,3]-rearrangement when treated with diethyl chlorophosphite, giving N -allenylphosphate 281 in a 78% yield.…”

Section: Reactions Of N-alkynyl Azolesmentioning

confidence: 99%

“…The chemistry of N -alkynyl azoles represents just a fraction of the nitrogen-substituted alkyne field. Over the years, there have been many reviews of ynamines [1,2,3] and ynamides [3,4,5,6], and some of these have included N -alkynyl azoles within their content; however, the only review that primarily focused on this class of compounds was published in 2004 [7], and in the last 15 years there has been a significant amount of work published in this area.…”

Section: Introductionmentioning

confidence: 99%

Preparation and Utility of N-Alkynyl Azoles in Synthesis

Reinus

Kerwin

2019

Molecules

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Heteroatom-substituted alkynes have attracted a significant amount of interest in the synthetic community due to the polarized nature of these alkynes and their utility in a wide range of reactions. One specific class of heteroatom-substituted alkynes combines this utility with the presence of an azole moiety. These N-alkynyl azoles have been known for nearly 50 years, but recently there has been a tremendous increase in the number of reports detailing the synthesis and utility of this class of compound. While much of the chemistry of N-alkynyl azoles mirrors that of the more extensively studied N-alkynyl amides (ynamides), there are notable exceptions. In addition, as azoles are extremely common in natural products and pharmaceuticals, these N-alkynyl azoles have high potential for accessing biologically important compounds. In this review, the literature reports of N-alkynyl azole synthesis, reactions, and uses have been assembled. Collectively, these reports demonstrate the growth in this area and the promise of exploiting N-alkynyl azoles in synthesis.

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“…4.8 eV). To determine the cyclopropenone decarbonylation photochemical reaction, we calculated the excitation energy using TD-DFT and CASSCF (8,6). Table 7 depicts the excitation energy, energy gap, and activation energy of cyclopropenone.…”

Section: Excited States Of Cyclopropenonementioning

confidence: 99%

“…Despite the fact that cyclopropenones are three-membered rings with sp 2 -hybridized carbon atoms, they are also characterized by having high thermal stability [4,5]. Extensive experimental and theoretical work has been devoted to the study of the chemical reactivity of cyclopropenones [6][7][8]. The results have suggested that the photochemical and thermal decomposition of cyclopropenones in the gas phase, in solution, or in the presence of various catalysts [9] yields carbon monoxide and acetylene (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation of the photochemical reaction mechanism of cyclopropenone decarbonylation

2011

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The gas-phase decomposition mechanism of the photochemical and thermal reaction of cyclopropenone leading to carbon monoxide and acetylene has been investigated theoretically. We employed the B3LYP, MP2, and CASSCF methods with the 6-311 þ G** basis set to determine the pathways and the potential energy surface (PES) of this reaction. PES minima were characterized by the absence of any imaginary frequencies and compared with the transition states that contained single imaginary frequencies. The intrinsic reaction coordinate (IRC) method was used to find the minimum energy paths in which reactants and products were connected to the transition states. Activation barrier, thermodynamic, and IRC analyses were performed using the above three methods. Our computations indicated that the decomposition of cyclopropenone proceeds through a stepwise mechanism containing two transition states (TS1 and TS2) and an intermediate. The results show that TS1, the critical transition state, determines the rate of the cyclopropenone decomposition reaction. Therefore, we employed natural bond order (NBO) calculations to probe the structure of the intermediate. The calculations showed that the intermediate has resonance structures containing a carbene and a zwitterion. Our results are in good agreement with previous theoretical and experimental studies.

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Reactive species: Ynols and ynamines

Cited by 22 publications

References 33 publications

Cyclopropenone-caged Sondheimer diyne (dibenzo[a,e]cyclooctadiyne): a photoactivatable linchpin for efficient SPAAC crosslinking

Cyclopropenone-caged Sondheimer diyne (dibenzo[a,e]cyclooctadiyne): a photoactivatable linchpin for efficient SPAAC crosslinking

Preparation and Utility of N-Alkynyl Azoles in Synthesis

Theoretical investigation of the photochemical reaction mechanism of cyclopropenone decarbonylation

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