ChemInform Abstract: Recent Advances in the Prins Cyclization

Greco, Sandro J.; Fiorot, Rodolfo G.; Lacerda, Valdemar; Santos, Reginaldo Bezerra dos

doi:10.1002/chin.201514302

Cited by 13 publications

(17 citation statements)

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“…This powerful methodology for formation of C-C bonds is also useful to produce substances such as 1,3-diol, β-halohydrin, allylic alcohols and tetrahydropyran (Scheme 1). 12 Control of experimental conditions is extremely important to reach the desired product with high selectivity. 1,3-Dioxanes, for example, can be synthesized with an excess of suitable aldehyde in presence of an acid catalyst.…”

Section: Introductionmentioning

confidence: 99%

“…1,3-Dioxanes, for example, can be synthesized with an excess of suitable aldehyde in presence of an acid catalyst. 12 It has been well established that either strong Lewis (e.g., TiCl 4 , TiBr 4 , InCl 3 , SnCl 4 , BF 3 .OEt 2 ) [13][14][15][16][17][18] or Brønsted acids (e.g., H 2 SO 4 , trifluoroacetic acid, p-toluenesulfonic acid, triflic acid) [19][20][21][22] have to be employed to the effective synthesis of these heterocycles. Some studies have demonstrated that concomitant usage of both types of acid catalysts has positive synergistic effect.…”

Section: Introductionmentioning

confidence: 99%

“…13 Computational studies have been done to rationalize the formation of 1,3-dioxanes via Prins cyclization, as well as to justify the chemo-, regio-and stereoselectivity. 12,25,26 The mechanism of the classical Prins reaction has usually been supposed to pass through cationic species, such as carbocations, mainly in aqueous media. Recently, Yamabe et al 27 warned that such ionic intermediates might not be found in the minimum energy path in presence of water, suggesting a hemiacetal as an unprecedentedly less energetic new intermediate (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

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Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Fiorot

Rambabu²,

Vijayakumar

et al. 2019

J. Braz. Chem. Soc.

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Density functional theory calculations (ωB97X-D/6-311++G(d,p)) are employed to investigate an alternative pathway for Prins-like cyclization. Although strong acids usually catalyze this reaction, 4-amino-1,3-dioxanes are rapidly obtained in high yields without catalyst when benzenamines and acetaldehyde react at low temperatures, in aqueous medium. Considering these conditions, we applied a supermolecule model with explicit water molecules to compute the mechanism for 4-amino-1,3-dioxanes formation from the reactants. The structure of the primary solvation shell was determined by Metropolis Monte Carlo method. In the Prins-cyclization step, we found an unpredicted pathway with non-ionic transition structures or intermediates. Explicit water molecules establish a net of hydrogen bonds allowing prototropism, maintaining the electrical neutrality in the system while two protons transfer occurs. To provide data to further experimental confirmation of this hypothesis, we estimated the kinetic isotope effect for the reaction. We also investigated the use of aliphatic amines, which indicates that the reaction may be of a broader application than first observed experimentally.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Fiorot

Rambabu²,

Vijayakumar

et al. 2019

J. Braz. Chem. Soc.

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“…Of the variety of methods developed, Prins-type cyclization of homoallylic amines/alcohols with carbonyl compounds would be one of the most attractive strategies for the formation of these heterocycles. Since the first publication of H 2 SO 4 -mediated addition of formaldehyde to alkenes by Prins, considerable work has been carried out to expand the application scope of this transformation: different Brønsted and Lewis acids such as TfOH, p -TSA, TFA, HF, BF 3 , FeX 3 , Sc(OTf) 3 , Ga(III), In(III), I 2 , Au(I), and TMSOTf have been successfully applied in Prins-type cyclization reactions. Further, Prins reactions have also been used as key steps for the syntheses of an increasing number of natural products .…”

Section: Introductionmentioning

confidence: 99%

Preparation of trans-2-Substituted-4-halopiperidines and cis-2-Substituted-4-halotetrahydropyrans via AlCl₃-Catalyzed Prins Reaction

Liu

Cui

et al. 2016

J. Org. Chem.

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A general and practical method for the preparation of trans-2-substituted-4-halopiperidines and cis-2-substituted-4-halotetrahydropyrans is reported. Using 5 mol % of AlCl3 as the catalyst and 2 equiv of trimethylsilyl halides as the halide sources, aza-Prins cyclization of N-tosyl homoallylamine or Prins cyclization of homoallylic alcohol with carbonyl compounds could be readily realized, giving the corresponding trans-2-substituted-4-halopiperidines or cis-2-substituted-4-halotetrahydropyrans in high yields and satisfactory diastereoselectivity.

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“…The Prins reaction of aldehydes and homoallylic alcohols mediated by Lewis and Brönsted acids has been used for the synthesis of substituted tetrahydropyrans in conventional target-oriented syntheses . The reaction has also been used in three-component combinatorial and diversity-oriented syntheses for acquiring substituent-based diversity .…”

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confidence: 99%

Three-Component, Diastereoselective Prins–Ritter Reaction for cis-Fused 4-Amidotetrahydropyrans toward a Precursor for Possible Neuronal Receptor Ligands

et al. 2016

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Here, we report an unprecedented, highly diastereoselective Prins-Ritter reaction of aldehydes, homoallylic alcohols, and nitriles in a three-component coupling reaction for the synthesis of tetra-cis-substituted 4-amidotetrahydropyrans. In this study, the reaction was not only applied for carbohydrate-based heterobicycles but also for more complex heterotricycles, showing acceptable levels of conversion yield (42-97% BRSM) and exclusive diastereoselectivity. Furthermore, the latter heterotricycles were converted to nine analogues of our neuronal receptor ligands IKM-159 and MC-27. An in vivo assay by intracerebroventricular injection in mice suggested that the substituent at C9 of the novel analogues interferes with the molecular interactions with the AMPA receptor, which was originally observed in the complex of IKM-159 and the GluA2 ligand binding domain. Our research has thus shown the power of a multicomponent coupling reaction for the preparation of a structurally diverse compound collection to study structure-activity relationships of biologically active small molecules.

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ChemInform Abstract: Recent Advances in the Prins Cyclization

Abstract: Review: 69 refs.

Cited by 13 publications

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Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Preparation of trans-2-Substituted-4-halopiperidines and cis-2-Substituted-4-halotetrahydropyrans via AlCl₃-Catalyzed Prins Reaction

Three-Component, Diastereoselective Prins–Ritter Reaction for cis-Fused 4-Amidotetrahydropyrans toward a Precursor for Possible Neuronal Receptor Ligands

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ChemInform Abstract: Recent Advances in the Prins Cyclization

Abstract: Review: 69 refs.

Cited by 13 publications

References 0 publications

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Alternative Non-Ionic Pathway for Uncatalyzed Prins Cyclization: DFT Approach

Preparation of trans-2-Substituted-4-halopiperidines and cis-2-Substituted-4-halotetrahydropyrans via AlCl3-Catalyzed Prins Reaction

Three-Component, Diastereoselective Prins–Ritter Reaction for cis-Fused 4-Amidotetrahydropyrans toward a Precursor for Possible Neuronal Receptor Ligands

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Preparation of trans-2-Substituted-4-halopiperidines and cis-2-Substituted-4-halotetrahydropyrans via AlCl₃-Catalyzed Prins Reaction