Direct cycle between co-product and reactant: an approach to improve the atom economy and its application in the synthesis and protection of primary amines

Guan, Qı; Jiang, Mingyang; Wu, Junhui; Zhai, Yanpeng; Wu, Yue; Bao, Kai; Zhang, Weige

doi:10.1039/c6gc01318j

Cited by 14 publications

(5 citation statements)

References 34 publications

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“…Furthermore, the potential sustainability improvements of this reaction could not be progressed further in this study. Unless the generation of toxic byproducts can be mitigated and waste products be regenerated in the Delépine reaction, the authors recommend that those seeking to utilize methods of amine formation look toward higher atom economy methods. − If the use of legacy methodology such as the Delépine reaction is required, then at least the use of chloroform can from this point forward be avoided.…”

Section: Discussionmentioning

confidence: 99%

Assessing the Limits of Sustainability for the Delépine Reaction

Jordan

Huang

Sneddon

et al. 2020

ACS Sustainable Chem. Eng.

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Herein, we report our efforts to improve the sustainability of the Delépine reaction for the formation of primary amines from activated alkyl halides. A number of alternative greener, more sustainable solvents to the traditionally employed chloroform were identified, and the use of dimethyl carbonate (DMC) as a solvent was exemplified in the synthesis of a number of pharmaceutically relevant building blocks including the 40 mmol scale synthesis of N-Boc-3-pyrroline. Green chemistry metrics were calculated to identify areas of the Delépine reaction that could potentially be improved upon. Poor atom economy (A.E.) was identified as a key shortcoming of this methodology, although our efforts to improve A.E. and reduce waste were unfortunately unsuccessful. A preliminary thermal safety evaluation was conducted using differential scanning calorimetry due to stability concerns raised over the nature of the products; none of the products were considered to have shock-sensitive or explosive propagating properties. The limits of potential sustainability improvements that could be achieved are critically discussed including the inherent issues with this methodology such as the release of formaldehyde, generation of carcinogenic bis(chloromethyl)ether, and poor atom economy.

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Section: Discussionmentioning

confidence: 99%

Assessing the Limits of Sustainability for the Delépine Reaction

Jordan

Huang

Sneddon

et al. 2020

ACS Sustainable Chem. Eng.

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“…Yellow crystalline solid, mp 171–173 °C, 1 H NMR (500 MHz, DMSO- d 6 ): δ 11.36 (s, 1H), 7.48–7.51 (m, 6H), 7.45–7.47 (m, 4H). Known compound …”

Section: Methodsmentioning

confidence: 99%

Approach to the Synthesis of Unsymmetrical/Symmetrical Maleimides via Desulfitative Arylation at Different Temperatures

et al. 2020

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“…[8] Similarly, other authors have described several processes in which the byproduct participates as a reagent in a subsequent step. [9] However, until our preliminary report, [10] no examples had been reported about the reuse of a byproduct as reactant being embodied into the final compound. [11] By its part, N-heterocycles are privileged motifs extensively present in both natural products and biologically active synthetic compounds.…”

Section: Introductionmentioning

confidence: 99%

Molybdenum‐Catalyzed One‐Pot Multi‐Step Synthesis of N‐Polyheterocycles from Nitroarenes and Glycols

Gómez‐Gil,

Cases,

Hernández‐Ruiz

et al. 2024

Eur J Org Chem

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We report the efficient, sustainable one‐pot synthesis of a wide variety of N‐polyheterocycles, such as imidazo‐quinolines and quinoxalines, and furoquinolines, from easily available nitroaromatics and glycols via a molybdenum catalytic domino reduction‐imine formation‐intramolecular cyclization‐oxidation sequence. It is worth highlighting that the recycling and incorporation of the waste carbonyl byproduct, generated in the reduction step, into the final compound is realized. In addition, the overall efficiency and atom economy of the process are further improved owing to the participation of one reaction intermediate as reductant that allows lowering the amount of external reducing agent employed.

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Direct cycle between co-product and reactant: an approach to improve the atom economy and its application in the synthesis and protection of primary amines

Abstract: Recoverable 3,4-diphenylmaleic anhydride for the atom-economical synthesis and protection of primary amines.

Cited by 14 publications

References 34 publications

Assessing the Limits of Sustainability for the Delépine Reaction

Assessing the Limits of Sustainability for the Delépine Reaction

Approach to the Synthesis of Unsymmetrical/Symmetrical Maleimides via Desulfitative Arylation at Different Temperatures

Molybdenum‐Catalyzed One‐Pot Multi‐Step Synthesis of N‐Polyheterocycles from Nitroarenes and Glycols

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