Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

Zhang, Wei; Qiao, Yan; Wang, Yang; Tang, Mingsheng; Wei, Donghui

doi:10.1002/qua.25367

Cited by 18 publications

(6 citation statements)

References 75 publications

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“…In 2017, Wei presented a theoretical investigation of the detailed mechanism and stereoselectivity of phosphine-catalyzed annulation of MBH carbonates with C , N -cyclic azomethine imines (Scheme 571). 636 In general, there are six steps in the catalytic cycle. The reaction begins with nucleophilic addition of the chiral phosphine to the MBH carbonate.…”

Section: Nucleophilic Phosphine Catalysis Of Mbh-alcohol Derivatives mentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Nucleophilic Phosphine Catalysis Of Mbh-alcohol Derivatives mentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…The previous theoretical work has provided evidence that Lewis base can not only act as base but also work as nucleophile. ,,,− To confirm the role of Lewis base DBU, we have performed global reactivity index (GRI) analysis of the related reactants and intermediates. Table provides the electrophilicity index ω, , electronic chemical potential μ, chemical hardness η, energies of highest occupied molecular orbital (HOMO) ( E H ) and lowest unoccupied molecular orbital (LUMO) ( E L ), and nucleophilicity index N . ,− The nucleophilicity index N , which is based on tetracyanoethylene (TCNE) taken as a reference, is defined as N = E HOMO(2) – E HOMO(TCNE) .…”

Section: Results and Discussionmentioning

confidence: 99%

Theoretical Study on DBU-Catalyzed Insertion of Isatins into Aryl Difluoronitromethyl Ketones: A Case for Predicting Chemoselectivity Using Electrophilic Parr Function

Wei

2017

ACS Omega

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The possible mechanisms of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU)-catalyzed chemoselective insertion of N -methyl isatin into aryl difluoronitromethyl ketone to synthesize 3,3-disubstituted and 2,2-disubstituted oxindoles have been studied in this work. As revealed by calculated results, the reaction occurs via two competing paths, including α and β carbonyl paths, and each path contains five steps, that is, nucleophilic addition of DBU to ketone, C–C bond cleavage affording difluoromethylnitrate anion and phenylcarbonyl–DBU cation, nucleophilic addition of difluoromethylnitrate anion to carbonyl carbon of N -methyl isatin, acyl transfer process, and dissociation of DBU and product. The computational results suggest that nucleophilic additions on different carbonyl carbons of N -methyl isatin via α and β carbonyl paths would lead to different products in the third step, and β carbonyl path associated with the main product 3,3-disubstituted oxindole is more energetically favorable, which is consistent with the experimental observations. Noteworthy, electrophilic Parr function can be successfully applied for exactly predicting the activity of reaction site and reasonably explaining the chemoselectivity. In addition, the distortion/interaction and noncovalent interaction analyses show that much more hydrogen bond interactions should be responsible for the lower energy of the transition state associated with β carbonyl path. The obtained insights would be valuable for the rational design of efficient organocatalysts for this kind of reactions with high selectivities.

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“…In the past decades, density functional theory (DFT) has been extensively used as a powerful method to explore the detailed reaction mechanisms, and predict the regioselectivity as well as chemoselectivities in organocatalytic and biological reactions . It is worth mentioning that the DABCO‐catalyzed [2+4] cycloaddition of ethyl allenoate with arylidenoxindole has been theoretically investigated, but the observed regioselectivity is remarkably different from the reaction in this paper.…”

Section: Introductionmentioning

confidence: 93%

Mechanisms and regioselectivities of DABCO/DMAP‐catalyzed [2+4] annulation reactions of allenoate with α,β‐unsaturated cyclic ketimine: A DFT study

Yang

Zhang

Zhao

et al. 2018

J of Physical Organic Chem

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In the present study, the reaction mechanisms as well as regioselectivities of 1,4-diazabicyclo-[2.2.2] octane (DABCO) and 4-dimethylaminopyridine (DMAP)-catalyzed [2+4] annulation reactions of allenoate with α,βunsaturated cyclic ketimine leading to hydropyridine derivatives have been theoretically investigated using density functional theory (DFT). In general, the amine catalyst can initiate the reaction by nucleophilic attack to allenoate leading to zwitterionic intermediate, which can then react with cyclic ketimine following different reaction mechanisms. For DABCO-catalyzed annulation, the α-attack is more energetically favorable, and the subsequent two consecutive proton transfers followed by intramolecular cyclization along with catalyst regeneration can lead to the α,β-[2+4] cycloadduct. While for DMAP-catalyzed annulation, γ-attack is preferred, and the subsequent intramolecular cyclization followed by catalyst regeneration results into the β,γ-[2+4] cycloadduct. The calculated results are consistent with the experimental observations. Further noncovalent interaction (NCI) analyses reveal that the steric repulsion, hydrogen bond interactions, and intramolecular C─H···π interactions as well as π-π interactions would be responsible for the observed regioselectivities.

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Theoretical investigation toward organophosphine‐catalyzed [3 + 3] annulation of Morita–Baylis–Hillman carbonates with azomethine imines: Mechanism, origin of stereoselectivity, and role of catalyst

Cited by 18 publications

References 75 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Theoretical Study on DBU-Catalyzed Insertion of Isatins into Aryl Difluoronitromethyl Ketones: A Case for Predicting Chemoselectivity Using Electrophilic Parr Function

Mechanisms and regioselectivities of DABCO/DMAP‐catalyzed [2+4] annulation reactions of allenoate with α,β‐unsaturated cyclic ketimine: A DFT study

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