Phenylaziridine as a Masked 1,3 Dipole in Reactions with Nonactivated Alkenes

Ungureanu, Ioana; Klotz, Philippe; Mann, André

doi:10.1002/1521-3773(20001215)39:24<4615::aid-anie4615>3.0.co;2-v

Cited by 89 publications

(19 citation statements)

References 16 publications

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“…Notably, the lack of minor product formation under experimental conditions reiterates the importance of incipient carbocationic stabilization by the presence of phenyl or aryl rings in the aziridine molecule. 29 The stability enjoyed by the incipient carbocation from the presence of a -Ph group is critical for the excellent regioselectivity, since alkyl substituted aziridines have been reported to exhibit poor regioselectivity under Lewis-acid mediated-or catalysed conditions. 30 Given the discussed stability of the phenyl substituted carbon, it can be hypothesized that the incorporation of more electron donating groups at the para-position of the phenyl ring will increase the incipient carbocationic stability, 31 thus increasing the rate of the ringopening process.…”

Section: Resultsmentioning

confidence: 99%

A computational study to unravel the selectivity in an iron-catalysed [3 + 2] cycloaddition of aziridine and heterocumulenes

Adhikari

2015

RSC Adv.

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Section: Resultsmentioning

confidence: 99%

A computational study to unravel the selectivity in an iron-catalysed [3 + 2] cycloaddition of aziridine and heterocumulenes

Adhikari

2015

RSC Adv.

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“…Among them, the transition‐metal‐catalyzed [3+2] cycloadditions of aziridines represent powerful tools enabling quick and efficient access to pyrrolidines in an atom‐economical fashion. However, almost all previous studies on this topic have been focused on 1,3‐dipolar cycloadditions of either aryl or alkyl aziridines by selective C−C, and C−N bond– cleavage with alkynes– or alkenes for the formation of pyrrolidine derivatives, substituted with saturated C−C bonds, in racemic form. In contrast, the [3+2] cycloaddition of an aziridine with an allene is rarely reported, and seriously limits the utilization of this method in the synthesis of the valuable 2‐methylene‐ and 3‐methylene‐pyrrolidines containing a C=C bond .…”

Section: Figurementioning

confidence: 99%

Regiodivergent Intermolecular [3+2] Cycloadditions of Vinyl Aziridines and Allenes: Stereospecific Synthesis of Chiral Pyrrolidines

et al. 2016

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The first rhodium-catalyzed intermolecular [3+ +2] cycloaddition reaction of vinyl aziridines and allenes for the synthesis of enantioenriched functionalizedp yrrolidines was realized. [3+ +2] cycloaddition with the proximalC =Cb ond of N-allenamides gave 3-methylene-pyrrolidines in high regioand diastereoselectivity,w hereas,2 -methylene-pyrrolidines were obtained as the major products by the cycloadditions of vinyl aziridines with the distal C=Cb ond of allenes.U se of readily available starting materials,abroad substrate scope, high selectivity,m ild reaction conditions,a sw ell as versatile functionalization of the cycloadducts make this approach very practical and attractive.

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“…[180] Also in 1999, Mann and co-workers used the same catalyst for the intermolecular cycloaddition of arylsubstituted aziridines with enol ethers, [181] and later demonstrated that this system could also be applied to non-activated alkenes (Scheme 7.28, B). [182] In these early works, high diastereoselectivity could be achieved only in the case of the formation of bicyclic five-five ring systems. In 2000, Nakagawa and Kawahara then reported the scandium-catalyzed cycloaddition of unsubstituted Cbz protected aziridines with skatole and used the method in a formal synthesis of physostigmine (Scheme 7.28, C).…”

Section: Formal [3+1] Cycloadditionsmentioning

confidence: 99%

Synthesis of Saturated Heterocycles via Metal-Catalyzed Formal Cycloaddition Reactions That Generate a C–N or C–O Bond

Waser

2013

Topics in Heterocyclic Chemistry

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In this section, the synthesis of saturated N-and O-heterocycles via formal cycloaddition is presented. The main focus is on metal-catalyzed reactions involving C-C or C-X  bond cleavage in three-or four-membered rings. After a fast presentation of pioneering works, the important breakthroughs of the last two decades are presented. The section starts with reactions involving three-membered rings. Formal [3+2] cycloadditions of donor-acceptor-substituted cyclopropanes and methylenecyclopropanes with carbonyls and imines are important methods to access tetrahydrofuran and pyrrolidine heterocycles. Formal [3+3] cycloadditions have emerged more recently. On the other hand, reactions of epoxides and aziridines with carbon monoxide or cumulenes are now well-established method to access heterocycles. These processes have been completed more recently with cycloaddition with olefins, carbonyls and imines. The section ends with the emerging field of four-membered ring activation for cycloaddition with  systems. This is the peer reviewed version of the following article: Top. Heterocycl. Chem. 2013, 32, 225, which The discovery of classical cycloaddition reactions, such as the (hetero) DielsAlder and 1,3-dipolar cycloadditions, has contributed tremendously to a more efficient access towards both carbocycles and heterocycles. The introduction of the term cycloaddition was necessary to distinguish these new types of reactions from previously discovered processes leading to cyclic structures, such as the famous Robinson annulation. In principle, each cycloaddition can be considered as a special case of the more general annulation process, but from which point on an annulation can be called a cycloaddition has been the topic of intensive discussions for decades, and is still not settled today. In 1968, Huisgen proposed a set of rules for the definition of cycloaddition, and the two first are still largely recognized as prerequisite: Although the rule that all the atoms of the starting materials have to be included in the product is not explicitly included in the definition, this requirement is usually recognized by most organic chemists. Even if electrocyclic cyclization processes were included in the original definition of Huisgen, the term cycloaddition is mostly used today for those reactions proceeding via the formation of at least two new bonds. Nevertheless, several researchers think that the term cycloaddition should be more strictly limited to reactions involving a continuous overlap of  electrons, and consequently allowing a concerted process. In fact, in his seminal publication, Huisgen already introduced further rules, in particular rule number 3, which explicitly stated that cycloadditions should not involve the cleavage of sigma bonds: -Huisgen Rule 3: "Cycloadditions do not involve the cleavage of  bonds." Unfortunately, in the same publication, Huisgen also described several reactions proceeding via -bond cleavage as cycloaddition. To solve this definition dilemma, several researchers have used th...

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Phenylaziridine as a Masked 1,3 Dipole in Reactions with Nonactivated Alkenes

Cited by 89 publications

References 16 publications

A computational study to unravel the selectivity in an iron-catalysed [3 + 2] cycloaddition of aziridine and heterocumulenes

A computational study to unravel the selectivity in an iron-catalysed [3 + 2] cycloaddition of aziridine and heterocumulenes

Regiodivergent Intermolecular [3+2] Cycloadditions of Vinyl Aziridines and Allenes: Stereospecific Synthesis of Chiral Pyrrolidines

Synthesis of Saturated Heterocycles via Metal-Catalyzed Formal Cycloaddition Reactions That Generate a C–N or C–O Bond

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