Improved synthesis of 2,4,6-trialkylpyridines from 1,5-diketoalkanes: the total synthesis of Anibamine

Miyakoshi, Takeru; Konno, Hiroyuki

doi:10.1039/c8ob02723d

Cited by 17 publications

(20 citation statements)

References 46 publications

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“…In our previous study, 2,4,6-trialkylpyridines were synthesized from alkyl-1,5-diketone derivatives by the refluxing them in AcOH 13 or HCl. 16 For this study, we did not attempt the synthesis of 4-, and 5-substituted alkylpyridine using that method.…”

Section: Resultsmentioning

confidence: 99%

“…All commercial reagents were of the highest purity available. 1 H (400, 500 or 600 MHz) and 13 C NMR (100, 125 or 150 MHz) spectra were recorded on JNM-ECX500 or JNM-ECA600 spectrometers.…”

Section: Methodsmentioning

confidence: 99%

“…8,9 Inspired by the pioneering work of Kaiser, 10 Piccialli, 11 and Knoevenagel,12 we developed methodology for the construction of pyridine frameworks 1 from 5-acetal-1-carbonyl substrates 2 via the corresponding oximes 3 without observable aldol-type side reactions. 13 Scheme 1 depicts our approach. Condensation of hydroxylamine with the carbonyl group of 2 gives oxime 3, which undergoes cyclization by attack of the nitrogen atom on the acetal carbon (upon its activation by AcOH to give the corresponding oxonium).…”

Section: Introductionmentioning

confidence: 99%

“…We also report the execution of this process in one pot, using 4 N HCl/dioxane instead of AcOH (Scheme 1). 13 Scheme 1. Acid-promoted synthesis of pyridine derivatives 1 from the corresponding simple-5-acetal-1-carbonyl compounds 2 by one-pot process Using this process as a key step, we achieved the total synthesis of anibamine, 13 a pyridinyl alkaloid isolated from Aniba sp.…”

Section: Introductionmentioning

confidence: 99%

“…13 Scheme 1. Acid-promoted synthesis of pyridine derivatives 1 from the corresponding simple-5-acetal-1-carbonyl compounds 2 by one-pot process Using this process as a key step, we achieved the total synthesis of anibamine, 13 a pyridinyl alkaloid isolated from Aniba sp. 14,15 In the present study, we further exemplify the utility of our method through the synthesis of four alkylpyridines (Scheme 2).…”

Section: Introductionmentioning

confidence: 99%

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Preparation of Pyridine Derivatives from the Corresponding 5-Acetal-1-carbonyl Compounds by Acid Promoted Cyclization

Konno¹,

Mihara²,

Watanabe³

2021

HETEROCYCLES

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Section: Resultsmentioning

confidence: 99%

“…All commercial reagents were of the highest purity available. 1 H (400, 500 or 600 MHz) and 13 C NMR (100, 125 or 150 MHz) spectra were recorded on JNM-ECX500 or JNM-ECA600 spectrometers.…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Preparation of Pyridine Derivatives from the Corresponding 5-Acetal-1-carbonyl Compounds by Acid Promoted Cyclization

Konno¹,

Mihara²,

Watanabe³

2021

HETEROCYCLES

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Terminal Alkynes as One‐Carbon Donors in [5+1] Heteroannulation: Synthesis of Pyridines via Ynimine Intermediates and Application in the Total Synthesis of Anibamine B

Lavernhe

Wang

2023

Angewandte Chemie

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heteroannulation of α,β-unsaturated oximes and their derivatives with alkynes has been developed into a powerful strategy for the synthesis of pyridines. It nevertheless lacks regioselectivity when unsymmetrically substituted alkynes are used. We report herein the unprecedented synthesis of polysubstituted pyridines by a formal [5+1] heteroannulation of two readily accessible building blocks. A copper-catalyzed aza-Sonogashira cross-coupling between β,γ-unsaturated oxime esters and terminal alkynes affords ynimines, which, without isolation, undergo an acid-catalyzed domino reaction involving ketenimine formation, 6π-electrocyclization and aromatization to afford pyridines. Terminal alkynes served as a one-carbon donor to the pyridine core in this transformation. Di-through pentasubstituted pyridines are accessible with complete regioselectivity and excellent functional-group compatibility. The first total synthesis of anibamine B, an indolizinium alkaloid with potent antiplasmodial activity, was accomplished featuring this reaction as a key step.

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Terminal Alkynes as One‐Carbon Donors in [5+1] Heteroannulation: Synthesis of Pyridines via Ynimine Intermediates and Application in the Total Synthesis of Anibamine B

Lavernhe

Wang

2023

Angew Chem Int Ed

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Transition‐metal‐catalyzed [4+2] heteroannulation of α,β‐unsaturated oximes and their derivatives with alkynes has been developed into a powerful strategy for the synthesis of pyridines. It nevertheless lacks regioselectivity when unsymmetrically substituted alkynes are used. We report herein the unprecedented synthesis of polysubstituted pyridines by a formal [5+1] heteroannulation of two readily accessible building blocks. A copper‐catalyzed aza‐Sonogashira cross‐coupling between β,γ‐unsaturated oxime esters and terminal alkynes affords ynimines, which, without isolation, undergo an acid‐catalyzed domino reaction involving ketenimine formation, 6π‐electrocyclization and aromatization to afford pyridines. Terminal alkynes served as a one‐carbon donor to the pyridine core in this transformation. Di‐ through pentasubstituted pyridines are accessible with complete regioselectivity and excellent functional‐group compatibility. The first total synthesis of anibamine B, an indolizinium alkaloid with potent antiplasmodial activity, was accomplished featuring this reaction as a key step.

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Improved synthesis of 2,4,6-trialkylpyridines from 1,5-diketoalkanes: the total synthesis of Anibamine

Abstract: Many pyridine syntheses have been developed to date. In this study, we focused on pyridine synthesis with 1,5-diketone derivatives and hydroxylamine.

Cited by 17 publications

References 46 publications

Preparation of Pyridine Derivatives from the Corresponding 5-Acetal-1-carbonyl Compounds by Acid Promoted Cyclization

Preparation of Pyridine Derivatives from the Corresponding 5-Acetal-1-carbonyl Compounds by Acid Promoted Cyclization

Terminal Alkynes as One‐Carbon Donors in [5+1] Heteroannulation: Synthesis of Pyridines via Ynimine Intermediates and Application in the Total Synthesis of Anibamine B

Terminal Alkynes as One‐Carbon Donors in [5+1] Heteroannulation: Synthesis of Pyridines via Ynimine Intermediates and Application in the Total Synthesis of Anibamine B

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