Highly Enantioselective Synthesis of Functionalized Glutarimide Using Oxidative N-Heterocyclic Carbene Catalysis: A Formal Synthesis of (−)-Paroxetine

Porey, Arka; Santra, Surojit; Guin, Joyram

doi:10.1021/acs.joc.9b00320

Cited by 21 publications

(5 citation statements)

References 59 publications

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“…Mostly known as convenient, air-stable precursors to N -heterocyclic carbenes (NHCs) used in organocatalytic transformations, − 1,2,4-triazolium salts also form upon deprotonation of NHC ligands for transition metal catalysts. − Beyond the field of catalysis, these 1,2,4-triazole-based ligands form phosphorescent cyclometalated complexes with the substituents on the carbene ligand being key to their tunable emission wavelengths, − while other late transition metal complexes containing 1,2,4-triazole ligands have shown promising in vitro anticancer activity in studies involving breast, colon, lung, skin, liver, and cervical cancer as well as leukemia. − N -Aryl-substituted 1,2,4-triazoles are also frequent building blocks in organic compounds with biological activity. − Although less common than imidazolium or 1,2,3-triazolium salts, 1,2,4-triazolium salts have been successfully used as ionic liquids for dissolving cellulose …”

Section: Introductionmentioning

confidence: 99%

Catalytic Preparation of 1-Aryl-Substituted 1,2,4-Triazolium Salts

et al. 2019

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1,4-Diaryl- and 1-aryl-4-alkyl-substituted 1,2,4-triazolium salts are convenient air-stable precursors to carbenes used both as organocatalysts or as ligands for transition metal complexes. Traditionally, they are prepared via a multistep synthetic pathway with the low-yielding formation of the triazolium ring occurring in the last step. We have developed an alternative two-step synthesis involving the conversion of a primary amine or aniline derivative to the corresponding 4-substituted triazole followed by a copper-catalyzed arylation with diaryliodonium salts. This transition metal-catalyzed arylation can be carried out under mild conditions in acetonitrile and is tolerant toward both water and oxygen. Additionally, the high functional group tolerance of the protocol described here gives easy access to triazolium salts containing heterocyclic substituents or sulfides.

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Section: Introductionmentioning

confidence: 99%

Catalytic Preparation of 1-Aryl-Substituted 1,2,4-Triazolium Salts

et al. 2019

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“…Thus, in a 2019 article by Porey et al, 24 the reaction of cinnamic aldehyde 8 with aryl-substituted malondiamide 12 in the presence of 10 mol% mesityl-substituted NHC catalysts was studied. They found that product 13 could be obtained with good stereoselectivity (91% ee , dr = 4:1) and 56% yield using DBU and oxidant III in tetrahydrofuran (Scheme 7 ).…”

Section: Michael Additionmentioning

confidence: 99%

Preparation of N- and C-Functionally-Substituted Glutarimides: A Review

Trukhanova¹,

Chernov²,

Kuvaeva³

et al. 2023

Synthesis

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Six-membered heterocyclic systems such as glutarimides are widely used in medicinal chemistry. The glutarimide skeleton is found in many commercially available pharmaceuticals due to a wide range of bioactivity. The preparation of C,N-highly functionalized glutarimides is an important topic in modern organic synthesis, since it reveals the ability to build a more complex system and thus expands the range of various drugs. This review describes approaches to the synthesis of N- and C-functionally-substituted glutarimides presented in the literature from 2005 to 2022. Options for the enantioselective synthesis of spiroglutarimides, the use of organocatalysis in the synthesis of glutarimides, and optimization of the synthesis of already known pharmaceuticals are described.1 Introduction2 Michael Addition2.1 Preparation of Glutarimides from Substituted Acrylamides and 1,3-Bielectrophiles2.2 Preparation of Glutarimides by the Reaction of Acetamide and α,β-Unsaturated Carbonyl Compounds2.2.1 Preparation of Glutarimides by the Reaction of Acetamide Derivatives and Acrolein Derivatives2.2.2 Preparation of Spiroglutarimides by the Reaction of Acetamide Derivatives and Bromacrolein Derivatives2.2.3 Preparation of Spiroglutarimides by the Reaction of Acetamide Derivatives and Acryloyl Cyanide Derivatives2.2.4 Preparation of Substituted Glutarimides Using Ytterbium Salts2.3 Michael Addition/Intramolecular Transacylation2.4 Preparation of Glutarimides from Baylis–Hillman Adducts3 Multicomponent Reactions4 Conclusion

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“…(Scheme 54). [81] Formation of enolate 46 from the enal-derived α,β-unsaturated acyl azolium via conjugate addition of the enolizable diamide, internal proton transfer/tautomerization and imide formation are salient steps of the postulated organocatalytic cycle.…”

Section: Cà C/cà N Cà N/cà N Cà S/cà N Bond Formation (Michael/lactam...mentioning

confidence: 99%

Oxidative N‐Heterocyclic Carbene Catalysis

Risi

Brandolese

Carmine

et al. 2022

Chemistry A European J

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N-Heterocyclic carbene (NHC) catalysis is a by now consolidated organocatalytic platform for a number of synthetic (asymmetric) transformations via diverse reaction modes/intermediates. In addition to the typical umpolung processes involving acyl anion/homoenolate equivalent species, implementation of protocols under oxidative conditions greatly expands the possibilities of this methodology. Oxidative NHC-catalysis allows for oxidative and oxygenative transformations through specific manipulations of Breslow-type species depending upon the oxidant used (external oxidant or O 2 /air), the derived NHC-bound intermediates paving the way to non-umpolung processes through activation of carbon atoms and heteroatoms. This review is intended to update the state of the art in oxidative NHCcatalyzed reactions that appeared in the literature from 2014 to present, with a strong focus to crucial intermediates and their mechanistic implications.

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Highly Enantioselective Synthesis of Functionalized Glutarimide Using Oxidative N-Heterocyclic Carbene Catalysis: A Formal Synthesis of (−)-Paroxetine

Cited by 21 publications

References 59 publications

Catalytic Preparation of 1-Aryl-Substituted 1,2,4-Triazolium Salts

Catalytic Preparation of 1-Aryl-Substituted 1,2,4-Triazolium Salts

Preparation of N- and C-Functionally-Substituted Glutarimides: A Review

Oxidative N‐Heterocyclic Carbene Catalysis

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