Ring Expansion of Vinylaziridines through the Strain-Release Pericyclic Reaction: Recent Developments and Applications

Heo, Yu Mi; Paek, Seung‐Mann

doi:10.3390/molecules18089650

Cited by 20 publications

(11 citation statements)

References 33 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The synthesis and reactivity of aziridines have been reviewed from time to time. 2,3 Some review articles focusing on specific type of aziridines such as aziridine-2-carboxylates, 4 2-haloaziridines, 5 2-methyleneaziridines, 6 and 2-vinylaziridines 7,8 have been published. This review paper aims to describe recent applications (2008 to early 2017) of aziridines, whether activated or non-activated, in synthesis of other heterocyclic frameworks by aziridine ring expansion.…”

Section: Introductionmentioning

confidence: 99%

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Singh¹,

Sudheesh²,

Keroletswe³

2017

Arkivoc

View full text Add to dashboard Cite

The inherent reactivity of the aziridine ring due to ring-strain makes it valuable building blocks for the synthesis of other heterocyclic motifs of biological relevance. Of particular significance is the generation of azomethine ylides from them and cycloaddition of ylides with alkenes, alkynes, and heterocumulenes. The ring undergoes opening followed by cyclization with a variety of reagents either in the presence of a catalyst or without any catalyst. This review article discusses the recent applications of aziridines in syntheses of four-to seven-membered heterocycles of biological relevance such as azetidines, 2

show abstract

Section: Introductionmentioning

confidence: 99%

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Singh¹,

Sudheesh²,

Keroletswe³

2017

Arkivoc

View full text Add to dashboard Cite

show abstract

“…Ring expansion of aziridines leading to six-membered rings through other processes than [2,3] [106] reported the total synthesis of (S)-coniine 188 from a homochiral methylene-aziridine 185. Nucleophilic ring opening is effected by a Grignard reagent in the presence of copper(I).…”

Section: Ring Expansions Of Nonactivated Aziridines and Azetidinesmentioning

confidence: 99%

“…The major one, oxazepine 226 arises from a [2,3] Meisenheimer rearrangement, which is the unique process when the oxygen atom is in a cis-relationship with the adjacent alkenyl moiety, and the minor one 227 is produced from the other trans diastereomer, through a [1,2] Meisenheimer rearrangement, giving rise to a transient isoxazoline, which is further oxidized to nitrone 227 (Scheme 60); note that 226 can be converted to the isoxazolidine by simple heating. This [2,3] Meisenheimer rearrangement served as a key step for the preparation of an analogue of (À)-debromoeudistomin K, a natural indolic alkaloid, which showed similar activity against the influenza virus compared to the natural molecule [117]. Our group recently reinvestigated this ring-expansion process of differently substituted azetidines into isoxazolidine through a [1,2] Meisenheimer rearrangement, in order to gain better knowledge of the issues of regio-and stereoselectivity of this reaction [118].…”

Section: Expansions Into Isoxazolidinesmentioning

confidence: 99%

“…The obtained regioisomer 146 is only explainable by a C-C bond cleavage producing a diradical 145 which finally cyclizes by recombination of the two-carbon atoms bearing the phenyl groups (Scheme 39). The [1,3] sigmatropic rearrangement of 2-vinylaziridines was also studied under activation by Lewis acids. Njardarson [89] demonstrated the feasibility of vinylaziridine-pyrroline conversion using copper(II) catalysis.…”

Section: Ring Expansions Of Nonactivated Aziridines and Azetidinesmentioning

confidence: 99%

“…1 of this chapter). Deprotonation at the N-Bn position is then selective and leads to an ylide with a trans-relationship with the adjacent alkenyl moiety, thus preventing any interaction between these moieties that would result in a [2,3] sigmatropic rearrangement leading to a seven-membered ring (see Sect. 3.2.3).…”

Section: Expansions Into Pyrroles Pyrrolidin-2-ones and Pyrrolidinesmentioning

confidence: 99%

See 2 more Smart Citations

Ring Expansions of Nonactivated Aziridines and Azetidines

Couty

David

2015

Topics in Heterocyclic Chemistry

View full text Add to dashboard Cite

Ring expansions promoted by ring strain in aziridines and azetidines are reviewed in this chapter, putting emphasis on recent applications from the last decade. This vast subject cannot be surveyed here exhaustively, and the reader will be guided to relevant precedent reviews or key reports. Rather, special attention will be put on selected examples and their mechanistic details, aiming to demonstrate that high selectivity can be reached in these reactions. In this issue, this fastgrowing topic has been divided into two distinct chapters, this one dealing with "nonactivated" aziridines and azetidines. Therefore, the reader will only find here examples involving NH-or N-alkylaziridines and N-azetidines as substrates for ring expansions, while N-acyl, N-carbamoyl, or N-tosyl compounds, defined as "activated" substrates, will be presented in the next chapter. This distinction can appear quite arbitrary at first sight but is amply justified by the great difference in reactivity of these distinct substrates. The first part focuses on the ring expansions of nonactivated aziridines into up to seven-membered rings and is further divided into expansions involving the incorporation of one (or more) heteroatoms, followed by ring expansions involving only incorporation of carbon atoms. The same model is then followed for azetidines.

show abstract

Transition Metal Aziridination Catalysts

Chandrachud

Jenkins

2017

Encyclopedia of Inorganic and Bioinorganic Chemistry

View full text Add to dashboard Cite

Aziridines are three‐membered rings containing one nitrogen and two carbon atoms. This functional group is present in many bioactive molecules in addition to being a useful synthetic intermediate that is analogous to epoxides. Since they are a strained ring system, aziridines are reactive toward nucleophilic ring opening, ring expansion, and ring rearrangement reactions. Due to their importance in synthetic chemistry, numerous approaches to their synthesis have been developed. In addition to traditional organic reaction approaches to aziridination, transition metal catalyzed versions of this reaction have been developed. The primary rationales for catalyzed aziridination includes broadening the substrate scope, increasing yields (particularly under mild conditions), and improving enantiomeric purity. These catalytic reactions can mostly be designated as one of three classes. In this article, each of these important transition metal catalyzed aziridination reaction paths will be reviewed in addition to the catalysts that perform them.

show abstract

Ring Expansion of Vinylaziridines through the Strain-Release Pericyclic Reaction: Recent Developments and Applications

Abstract: Recent syntheses of azetidines, pyrrolidines, piperidines and azepines through cycloaddition or sigmatropic rearrangements of vinylaziridines are described. Applications to natural product synthesis and mechanistic investigations are also summarized.

Cited by 20 publications

References 33 publications

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Recent applications of aziridine ring expansion reactions in heterocyclic synthesis

Ring Expansions of Nonactivated Aziridines and Azetidines

Transition Metal Aziridination Catalysts

Contact Info

Product

Resources

About