Chiral Heterocycles by Iminium Ion Cyclization

Royer, Jacques; Bonin, Martine; Micouin, Laurent

doi:10.1021/cr020083x

Cited by 399 publications

(156 citation statements)

References 466 publications

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“…The reaction starts by the formation of imine 4 which suffers an intramolecular nucleophilic attack by the thiol group from either side to furnish a diastereomeric mixture of 2-(substituted)thiazolidine-4-carboxylic acids. 40,41 The isomerization at C-4 of the thiazolidine via deprotonation/protonation is ruled out based on spectroscopic data (vide infra). It is believed that, under our conditions, the generation of azomethine ylide has not been formed and hence the chirality at C-4 remained unchanged.…”

Section: Resultsmentioning

confidence: 99%

“…36 The possible mechanism for thiohydantoins 12 started through the preferential attack of the thiazolidine nitrogen of 7 on phenyl isothiocyanate (11) from the opposite face to give the favourable thiourea derivatives 13 (K1>>K2) (Scheme 6). 40,51 However, such conformation of 13 prevents the formation of cis-thiohydantoins 14 and alternatively, the intermediate 15 would consequently lead to the trans-thiohydantoins 12.…”

Section: Methodsmentioning

confidence: 99%

“…[39][40][41][42][43] It seems that using our optimal conditions in the synthesis of 2-(substituted)thiazolidine-4-carboxylic acids affects both the experimental yield and diastereomeric ratio (Table). Thus, using such conditions afforded diastereomeric mixtures of 7 and 8 in 75-98% yields, and the cis-diastereomer 7 was obtained as the major product in all cases.…”

Section: Scheme 3 Synthesis Of 35-bis(2-nitrophenyl)tetrahydro-1h-tmentioning

confidence: 99%

See 2 more Smart Citations

New aspects of the formation of 2-substituted thiazolidine-4-carboxylic acids and their thiohydantoin derivatives

Mahdy¹,

Elboray²,

Fandy³

et al. 2017

Arkivoc

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Aromatic aldehydes reacted readily with (R)-cysteine in boiling acidified methanol to give diastereomeric mixtures of the corresponding 2-(aryl substituted) thiazolidine-4-carboxylic acids. 4-Nitrobenzaldehyde under similar conditions afforded one isomer of 2-(4-nitrophenyl)-thiazolidine-4-carboxylic acid, which epimerized in the NMR solvents into a diastereomeric mixture. 2-Nitrobenzaldehyde reacted with (R)-cysteine to afford 3,5-bis-(2-nitrophenyl)-tetrahydro-1H-thiazolo[3,4-c]oxazol-1-one as the sole product, which collapsed in the NMR solvent into a diastereomeric mixture of the thiazolidine-4-carboxylic acids. The thiazolidine derivatives reacted smoothly with phenyl isothiocyanate to give single isomers of the corresponding thiohydantoins.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Scheme 3 Synthesis Of 35-bis(2-nitrophenyl)tetrahydro-1h-tmentioning

confidence: 99%

See 1 more Smart Citation

New aspects of the formation of 2-substituted thiazolidine-4-carboxylic acids and their thiohydantoin derivatives

Mahdy¹,

Elboray²,

Fandy³

et al. 2017

Arkivoc

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“…而杂原子, 例如 O, S 和 N 同样可以作为亲核试剂, 可与环状亚胺正离子反应形成噁唑啉环、噻唑环和咪唑环等结构 [5] . 在药物化学研究领域, 氮杂多环是十分常见的结构片断, 因此研究如何构建这类结构, 特别是研究这类结构的手性构建有很大的实际应用意义 [25] .…”

Section: 色胺、丙炔酸酯和 αβ-不饱和醛三组份串联反应unclassified

Progress in Asymmetric Organocatalyzed Michael Addition/Hemi-aminoacetalization/Acylimminium-Cyclization Cascade Reactions

陈杰¹,

刘钦²,

戴小鸯³

et al. 2013

Chin. J. Org. Chem.

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During the last decades along with the development of asymmetric organocatalysis, tremendous achievements have been made in asymmetric organocatalytic domino or cascade reactions. Herein, the examples of domino or cascade reactions based on asymmetric organocatalyzed Michael addition are described. More specifically, this review aims to cover and discuss the hemi-aminoacetalyzation/acylimminium-cyclization initiated by Michael addition, and the application of this type of reactions in the synthesis of alkaloids.

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“…Among a variety of methods reported to date, the Pictet-Spengler reaction [29][30][31][32][33] is one that involves the acid-catalyzed condensation of an aldehyde with an aliphatic amine attached to a sufficiently reactive aromatic nucleus like 24 to form imine (25), which is often activated by acids. Endo cyclization between a carbon nucleophile of a sufficiently reactive aromatic moiety and the activated iminium ion results in a new C-C bond, forming a N-hetero-cyclic ring (26) (Scheme 5).…”

Section: Named Reaction On Solid-phase For the Synthesis Of Heterocyclesmentioning

confidence: 99%

Solid-phase organic synthesis of heterocyclic compounds

Izumi

2006

J. Pestic. Sci.

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The establishment of an efficient method of synthesizing heterocycles is required for the development of pharmaceuticals and agrochemicals, since many bioactive compounds have a heterocyclic ring. It is also necessary to prepare libraries of small organic compounds for investigations of function and the discovery of more bioactive compounds in pharmaceutical and agrochemical chemistry. Combinatorial and parallel synthetic methodologies provide the main driving force for the preparation of libraries for applications in the discovery of lead compounds and high-throughput medicinal chemistry within the pharmaceutical industry. [1][2][3] Many different formats of high-throughput chemistry are available and solid-phase organic synthesis (SPOS) plays a pivotal role allowing the convenient handling of large numbers of synthetic intermediates. 4,5) Since the combinatorial chemistry first appeared in the early 1990s, the way drugs are discovered has changed dramatically. The SPOS strategy has been a strong tool for high throughput synthesis and combinatorial chemistry.6-9) Synthetic intermediates are retained on the support and can be, therefore, quickly separated from the reaction mixture without extraction, concentration, and purification. SPOS is thus particularly advantageous for multi-step iterative synthesis. Various solid-phase automated synthesizers have been developed and are now commercially available. Even though several synthesizers for solution synthesis have been developed, automation is essentially easier in solid-phase synthesis than solution synthesis. In particular, the automated synthesis of peptides and oligonucleotides has allowed their facile and rapid preparation and greatly contributed to the elucidation of their functions. However, SPOS is not without its drawbacks since often extended development times are required to optimize new solid-phase chemical reactions. Actually, many laboratories have been engaged in the development of novel solidphase linking strategies and chemical technologies. This paper describes recent findings in, and a useful method for, the synthesis of heterocycle and nitrogen heterocycle compounds. Selenium-based solid-phase chemistry to include nitrogen-containing heterocyclesNicolaou and co-workers have been engaged in the development of novel solid-phase linking strategies and chemical technologies aimed at the construction of discovery-oriented, natural product-like libraries. [10][11][12] Toward this end, several natural product-like templates have been tethered to a solidsupport utilizing an intramolecular, selenium-mediated cycloaddition procedure. Encouraged by their success in developing chemistry and technology to produce natural productlike libraries of oxygen-containing heterocycles and carbocyclic frameworks [13][14][15][16] and due to the potential utility of such libraries in chemical biology investigations, 17,18) they sought to expand the scope of this selenium-based solid-phase chemistry to include nitrogen-containing heterocycles. Recently, they reported t...

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Chiral Heterocycles by Iminium Ion Cyclization

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 399 publications

References 466 publications

New aspects of the formation of 2-substituted thiazolidine-4-carboxylic acids and their thiohydantoin derivatives

New aspects of the formation of 2-substituted thiazolidine-4-carboxylic acids and their thiohydantoin derivatives

Progress in Asymmetric Organocatalyzed Michael Addition/Hemi-aminoacetalization/Acylimminium-Cyclization Cascade Reactions

Solid-phase organic synthesis of heterocyclic compounds

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