AgSbF<sub>6</sub>-Promoted Cycloaddition Reaction of 2-Trifluoromethyl-<i>N</i>-tosylaziridine with Aldehydes

Maeda, Ryo; Ishibashi, Rie; Kamaishi, Ryo; Hirotaki, Kensuke; Furuno, Hiroshi; Hanamoto, Takeshi

doi:10.1021/ol202697y

Cited by 49 publications

(10 citation statements)

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“…During the course of our efforts to explore the synthetic use of 2‐CF 3 ‐ N ‐Ts‐aziridine,8 we have recently reported the regioselective ring‐opening reaction of 1 with some nucleophiles under basic conditions 9. In this work, we carried out the reaction of 1 with an indole in the presence of t BuOK as a base under basic conditions to obtain the corresponding N1 adduct of the indole in excellent yield with complete regioselectivity (Table 1, entry 10).…”

Section: Methodsmentioning

confidence: 99%

Klassiker Organikum

2016

Chemie in nserer Zeit

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Incorporation of fluorine atoms into biologically active organic molecules often causes enhancement of activity, stability, and solubility, as well as reduction of toxicity. Tryptamine derivatives are known for important medicines concerning our mental health. Therefore, fluorinated tryptamine derivatives could be promising medicinal candidates for pharmaceutical chemistry. We have already reported the regioselective ring‐opening reaction of 2‐CF3‐N‐Ts‐aziridine (Ts=4‐toluenesulfonyl) with some nucleophiles. If this ring‐opening reaction proceeds smoothly at the C3 position of indoles, it could provide a solution for the synthesis of CF3‐containing tryptamine analogues. We examined the diethylzinc‐promoted direct C3 alkylation of indoles with 2‐CF3‐N‐Ts‐aziridine under basic conditions. We have developed the synthesis of CF3‐tryptamine from 2‐CF3‐N‐Ts‐aziridines and indoles by using diethylzinc as a base with excellent yields and complete regioselectivity.

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Section: Methodsmentioning

confidence: 99%

Klassiker Organikum

2016

Chemie in nserer Zeit

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“…In 2011, Hanamoto and co-workers finally reported the formal [3+2] cycloaddition of trifluromethyl substituted tosyl aziridines with aldehydes (Scheme 7.30, C). [191] This reaction proceeded also with C-N cleavage, but with opposite regioselectivity and high diastereoselectivity. As the trifluoromethyl group is not able to stabilize a carbocation 29 intermediate, the reaction starts most probably by a nucleophilic SN 2 -like attack of the carbonyl on the less substituted carbon of the aziridine.…”

Section: Formal [3+1] Cycloadditionsmentioning

confidence: 98%

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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“…Alternatively, Hanamoto et al have developed elegant methods giving rise to those heterocycles with a CF3 group at the 5-position but requiring nevertheless the prior preparation of trifluoromethylated aziridines. 12,13 Therefore, the development of novel synthetic methods that allow efficient and rapid access to trifluoromethylated imidazolines and oxazolidines is still highly desirable. Herein, we report an electrochemical three-components tandem process for the preparation of 4-(2,2,2-trifluoroethyl)-2-imidazolines and 4-(2,2,2-trifluoroethyl)-1,3-oxazolidines.…”

Section: Electrochemical Tandem Trifluoromethylation Of Allylamines /Formal (3+2)-cycloaddition For the Rapid Access To Cf 3 -Containing mentioning

confidence: 99%

Electrochemical tandem trifluoromethylation of allylamines/formal (3 + 2)-cycloaddition for the rapid access to CF₃-containing imidazolines and oxazolidines

2021

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AgSbF₆-Promoted Cycloaddition Reaction of 2-Trifluoromethyl-N-tosylaziridine with Aldehydes

Abstract: 2-Trifluoromethyl-N-tosylaziridine reacted with various aldehydes in the presence of a catalytic amount of AgSbF(6) to provide the corresponding cis-4-trifluoromethyl-2-substituted-N-tosyl-1,3-oxazolidines with excellent regio- and stereoselectivity.

Cited by 49 publications

References 44 publications

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

Electrochemical tandem trifluoromethylation of allylamines/formal (3 + 2)-cycloaddition for the rapid access to CF₃-containing imidazolines and oxazolidines

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AgSbF6-Promoted Cycloaddition Reaction of 2-Trifluoromethyl-N-tosylaziridine with Aldehydes

Abstract: 2-Trifluoromethyl-N-tosylaziridine reacted with various aldehydes in the presence of a catalytic amount of AgSbF(6) to provide the corresponding cis-4-trifluoromethyl-2-substituted-N-tosyl-1,3-oxazolidines with excellent regio- and stereoselectivity.

Cited by 49 publications

References 44 publications

Klassiker Organikum

Klassiker Organikum

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

Electrochemical tandem trifluoromethylation of allylamines/formal (3 + 2)-cycloaddition for the rapid access to CF3-containing imidazolines and oxazolidines

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AgSbF₆-Promoted Cycloaddition Reaction of 2-Trifluoromethyl-N-tosylaziridine with Aldehydes

Electrochemical tandem trifluoromethylation of allylamines/formal (3 + 2)-cycloaddition for the rapid access to CF₃-containing imidazolines and oxazolidines