Lewis Acid-Mediated Cycloaddition of Methylenecyclopropanes with Aldehydes and Imines:  A Facile Access to Indene, THF, and Pyrrolidine Skeletons via Homoallylic Rearrangement Protocol

Shi, Min; Xu, Bo; Huang, Jinwen

doi:10.1021/ol0498242

Cited by 90 publications

(17 citation statements)

References 19 publications

(14 reference statements)

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“…27). 12 Furthermore, the Lewis acid-catalyzed intramolecular endo-cyclization of trimethylsilyl methylenecyclopropyl imines 63 selectively gave the multisubstituted indolizidines 64 (eq. 28).…”

Section: Pyrroles From Mcpsmentioning

confidence: 99%

Heterocycles from methylenecyclopropanes

et al. 2015

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The discovery of a series of novel organic reactions has made methylenecyclopropanes (MCPs) some of the most popular building blocks in synthetic organic chemistry during the past two decades. Among reported works, the construction of heterocycles from MCPs has highlighted new synthetic methodologies that afford more opportunities for the quick synthesis of elaborately substituted products, and this should draw a great deal of attention. However, reviews in this area are insufficient, and the latest monograph on heterocycle synthesis from MCPs was published 12 years ago. This review aims to summarize the novel organic reactions of MCPs to produce heterocycles published in recent years, which have provided specific and powerful tools for organic synthesis.

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Section: Pyrroles From Mcpsmentioning

confidence: 99%

Heterocycles from methylenecyclopropanes

et al. 2015

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“…Finally, the use of Lewis acid to promote the cycloaddition between alkylidenecyclopropanes and carbonyl compounds has also been reported, but most reactions remain limited in scope or lead to mixture of products. [44][45][46][47] 7.2.1.1.2 C-N Bond Formation In a similar way as tetrahydrofurans are obtained via the [3+2] cycloaddition of cyclopropanes and carbonyls, pyrrolidines are generated from cyclopropanes and imines. It is consequently not surprising that many methods established in the case of carbonyls were later extended to imines.…”

Section: C-o Bond Formationmentioning

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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“…Another example of the reactivity of alkylidenecyclopropanes with amine derivatives was reported by Shi et al, in 2004. 27 Indeed, these authors showed that alkylidenecyclopropanes with diisopropyl azodicarboxylate (DIAD) or diethyl azodicarboxylate (DEAD) in acetonitrile under mild conditions in the presence of Zr(OTf) 4 R 1 = R 2 = Ph, R 3 = Me: 55% R 1 = Ph, R 2 = H, R 3 = Me: 51% R 1 = p-BrC 6 H 4 , R 2 = H, R 3 = Me: 48% R 1 = R 2 = Ph, R 3 = Bn: 60% R 1 = R 2 = Ph, R 3 = n-Pr: 49% R 1 = p-BrC 6 H 4 , R 2 = H, R 3 = n-Pr: 53% underwent ring-expansion reactions to give the corresponding cyclobutanones in good-to-high yields (57e99%).…”

Section: Ring-opening Reactions By Amine Derivativesmentioning

confidence: 99%

“…40 In addition, Shi et al have disclosed the reactions of alkylidenecyclopropanes with aldehydes, imines 41 FriedeleCrafts reaction mechanism and providing moderate-togood yields (42e85%). 43 In 2003, Kilburn et al reported the intermolecular addition of silylated methylenecyclopropanes to aldehydes mediated by BF 3 $Et 2 O to give mixtures of the corresponding simple tetrahydrofurans and furofurans in moderate yields.…”

Section: Ring-opening Reactions Through Alkylation or Acylationmentioning

confidence: 99%

Recent developments in the reactivity of methylene- and alkylidenecyclopropane derivatives

Pellissier

2010

Tetrahedron

141

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Lewis Acid-Mediated Cycloaddition of Methylenecyclopropanes with Aldehydes and Imines: A Facile Access to Indene, THF, and Pyrrolidine Skeletons via Homoallylic Rearrangement Protocol

Abstract: Methylenecyclopropanes (MCPs) 1 can react with aldehydes and aldimines to give the corresponding indene, THF, and pyrrolidine cycloaddition products in the presence of BF(3).OEt(2) under mild reaction conditions.

Cited by 90 publications

References 19 publications

Heterocycles from methylenecyclopropanes

Heterocycles from methylenecyclopropanes

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

Recent developments in the reactivity of methylene- and alkylidenecyclopropane derivatives

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