Divergent and Selective Functionalization of 2-Formylpyrrole  and its Application in the Total Synthesis of the Aglycone Alkaloid Pyrrolemarumine

Martínez-Mora, Eder I.; Caracas, Miguel A.; Escalante, Carlos H.; Madrigal, Damian A.; Quiroz-Florentino, Héctor; Delgado, Francisco; Tamariz, Joaquı́n

doi:10.29356/jmcs.v60i1.67

Cited by 4 publications

(7 citation statements)

References 23 publications

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“…The dehydration of the dihydropyrrole (aromatization) took place to afford Py-2-C ( 4 ) as the final product [ 4 , 5 , 6 ] ( Figure 1 ). The total synthesis of pyrrolemarumine ( 5 ) was attained by the regioselective functionalization of 2-formylpyrrole [ 7 ]. The biosynthesis of pyrrole consists of amino acids (glycine, proline, serine, threonine, and tryptophan) and dicarboxylic acids (malonic acid, oxaloacetic acid, and succinic acid) as synthons for the construction of the aromatic ring [ 8 ].…”

Section: Synthesis and Biosynthesis Of Pyrrole-2-carbaldehydesmentioning

confidence: 99%

Pyrrole-2-carboxaldehydes: Origins and Physiological Activities

Matsugo

Nakamura

2023

Molecules

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Pyrrole-2-carboxaldehyde (Py-2-C) derivatives have been isolated from many natural sources, including fungi, plants (roots, leaves, and seeds), and microorganisms. The well-known diabetes molecular marker, pyrraline, which is produced after sequential reactions in vivo, has a Py-2-C skeleton. Py-2-Cs can be chemically produced by the strong acid-catalyzed condensation of glucose and amino acid derivatives in vitro. These observations indicate the importance of the Py-2-C skeleton in vivo and suggest that molecules containing this skeleton have various biological functions. In this review, we have summarized Py-2-C derivatives based on their origins. We also discuss the structural characteristics, natural sources, and physiological activities of isolated compounds containing the Py-2-C group.

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Section: Synthesis and Biosynthesis Of Pyrrole-2-carbaldehydesmentioning

confidence: 99%

Pyrrole-2-carboxaldehydes: Origins and Physiological Activities

Matsugo

Nakamura

2023

Molecules

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“…It was decided to start with similar enaminones to test a new approach for the construction of indolizines. Therefore, 9a or 9b were reacted with the corresponding methyl or ethyl bromoacetates 7a and 7b under basic conditions to afford pyrroles 10a-c [42], which were reacted with DMFDMA to convert them into enaminones 12a-c (Scheme 6). Unfortunately, enaminone 12b was formed in a mixture of methyl esters as a result of transesterification with the methoxy ions in the reaction medium.…”

Section: Chemistrymentioning

confidence: 99%

Pyrrole-Based Enaminones as Building Blocks for the Synthesis of Indolizines and Pyrrolo[1,2-a]pyrazines Showing Potent Antifungal Activity

Miranda-Sánchez,

Escalante,

Andrade-Pavón

et al. 2023

Molecules

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As a new approach, pyrrolo[1,2-a]pyrazines were synthesized through the cyclization of 2-formylpyrrole-based enaminones in the presence of ammonium acetate. The enaminones were prepared with a straightforward method, reacting the corresponding alkyl 2-(2-formyl-1H-pyrrol-1-yl)acetates, 2-(2-formyl-1H-pyrrol-1-yl)acetonitrile, and 2-(2-formyl-1H-pyrrol-1-yl)acetophenones with DMFDMA. Analogous enaminones elaborated from alkyl (E)-3-(1H-pyrrol-2-yl)acrylates were treated with a Lewis acid to afford indolizines. The antifungal activity of the series of substituted pyrroles, pyrrole-based enaminones, pyrrolo[1,2-a]pyrazines, and indolizines was evaluated on six Candida spp., including two multidrug-resistant ones. Compared to the reference drugs, most test compounds produced a more robust antifungal effect. Docking analysis suggests that the inhibition of yeast growth was probably mediated by the interaction of the compounds with the catalytic site of HMGR of the Candida species.

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“…Pyrroles 8a-j were prepared through a straightforward and efficient route based on the functionalization of 2-formylpyrrole (13a), using recently described methodologies [41]. Firstly, 13a was reacted with the series of benzyl bromides 14a-d to produce adequately N-substituted five-membered aza-units 13b-e, respectively (Scheme 2), which were treated with the phosphonates 15a-c to afford derivatives 8a-f in high yields (Table 1, entries 1-6).…”

Section: Synthesismentioning

confidence: 99%

“…Due to our interest in transforming simple five-membered heterocycles into natural products [40,41] and complex azapolycyclic structures [42], we herein combined both approaches shown in Scheme 1 to design the construction of pentacycles 11, after carrying out an uncommon but highly diastereoselective Diels-Alder cycloaddition followed by a coupling reaction. This route also allowed out the aromatization of Scheme 1: Synthetic approaches for the preparation of pyrrolo-fused aza-hetero polycyclic frames.…”

Section: Introductionmentioning

confidence: 99%

Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole

Escalante

Martínez-Mora

Espinoza‐Hicks

et al. 2020

Beilstein J. Org. Chem.

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A highly regio-, chemo- and stereoselective divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles is herein described, starting from 2-formylpyrrole and employing Diels–Alder and Heck arylation reactions. 3-(N-Benzyl-2-pyrrolyl)acrylates and 4-(pyrrol-2-yl)butenones underwent a highly endo-Diels–Alder cycloaddition with maleimides to furnish octahydropyrrolo[3,4-e]indoles, which served as precursors in the regioselective synthesis of aza-polycyclic skeletons via an intramolecular Heck arylation reaction. Through the latter reaction, the 3-(N-benzyl-2-pyrrolyl)acrylates give rise to 3-(pyrrolo[2,1-a]isoindol-3-yl)acrylates. A further oxidative aromatization of the polycyclic intermediates provides the corresponding polycyclic pyrrolo-isoindoles and isoindolo-pyrrolo-indoles. A theoretical study on the stereoselective Diels–Alder reactions, carried out by calculating the endo/exo transition states, revealed the assistance of non-covalent interactions in governing the endo stereocontrol.

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Divergent and Selective Functionalization of 2-Formylpyrrole and its Application in the Total Synthesis of the Aglycone Alkaloid Pyrrolemarumine

Cited by 4 publications

References 23 publications

Pyrrole-2-carboxaldehydes: Origins and Physiological Activities

Pyrrole-2-carboxaldehydes: Origins and Physiological Activities

Pyrrole-Based Enaminones as Building Blocks for the Synthesis of Indolizines and Pyrrolo[1,2-a]pyrazines Showing Potent Antifungal Activity

Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole

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