ChemInform Abstract: Efficient Synthesis of (.+‐.)‐Horsfiline Through the MgI<sub>2</sub>‐Catalyzed Ring‐Expansion Reaction of a Spiro[cyclopropane‐1,3′‐indol]‐2′‐one.

Fischer, Christian; Meyers, Christiane; Carreira, Erick M.

doi:10.1002/chin.200037216

Cited by 7 publications

(7 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The practicality of the hypothesis was first exemplified by Carreira and co-workers in synthesizing (±)-horsfiline, a naturally occurring oxindole-based alkaloid, extracted from the leaves of Horsfieldia superba ( Scheme 14 ). 19 The authors implemented 1,3,5-trimethyl-1,3,5-triazinane 31 as a synthetic equivalent for N -methylmethanamine and MgI 2 as a bifunctional catalyst, wherein the synergistic operation by the Lewis acidic metal center and nucleophilic iodide led to facile ring opening of spirocyclopropane, thereby facilitating annulation with an imine to afford the cyclic adduct 32 , which then furnished (±)-horsfiline by the removal of the protecting group.…”

Section: Spirocyclopropyl Oxindolesmentioning

confidence: 99%

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

et al. 2020

View full text Add to dashboard Cite

Spirocyclopropane represents a privileged structural scaffold for accessing synthetic libraries of densely functionalized spirocarbo- and heterocyclic compounds. Due to the ubiquity of spirocyclic motifs as a potent pharmacophore in natural products and pharmaceuticals, recent years have witnessed significant advances in developing synthetic strategies that exploits carbon–carbon bond scission in spirocyclopropanes. This paper summarizes the recent developments in stereoselective ring expansion of spirocyclopropanes in diversity-oriented synthesis and highlights the synthetic as well as mechanistic rationale of those methodologies. This review also encompasses the applicability of the protocols in bioactive natural product syntheses.

show abstract

Section: Spirocyclopropyl Oxindolesmentioning

confidence: 99%

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

et al. 2020

View full text Add to dashboard Cite

show abstract

“…The generated enolate I would then add onto the imine, followed by cyclization via an SN 2 process. The broad potential of the method was further demonstrated in the total synthesis of spiroxindole alkaloids, including horsfiline, [49] strychnofoline, [50][51] and spyrotry-10 prostatin B, [52][53] as well as in the production of small molecule libraries with a pyrrolidine core. [54][55][56][57][58][59][60][61] Scheme 7.8: MgI2-catalyzed [3+2] annulation of cyclopropanes with imines and application in the total synthesis of spiroxindole alkaloids.…”

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

View full text Add to dashboard Cite

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...

show abstract

“…In this paper, the molecular structure and electronic properties of 2, 18,19,20,20.01,8.03,7.09,14.024,11,13,17(31),18,24,26, were calculated by the B3LYP density functional model using 6-31G, 6-311G, 6-311++G and 6-311++G(d,p) basis sets. B3LYP calculation results indicated some selected bond length and bond angle values for this molecule.…”

Section: Introductionmentioning

confidence: 99%

“…For example, spirotryprostatin B, a natural alkaloid isolated from the fermentation broth of aspergillus fumigatus, has been identified as a novel inhibitor of microtubule assembly, and pteropodine and isopteropodine have been shown to modulate the function of muscarinic serotonin receptors. The interesting structural array and the highly pronounced pharmacological activity displayed by the class of spirooxindole compounds have made them attractive synthetic compounds [13][14][15][16]. Azaspiro derivatives are well-known [17][18][19], but the preparation of the corresponding oxa analogues has evolved at a relatively slow pace [20].…”

Section: Introductionmentioning

confidence: 99%

Computational Studies and Energies for the Dioxa-Pentaazaheptacyclo-Hentriaconta-Octaen-One through Density Functional Theory and Natural Bond Orbital

Shahbazi¹,

Ghammamy²

2014

UCMS

View full text Add to dashboard Cite

Abstract:In this paper, the molecular structure and electronic properties of 2, 18,19,20,20.01,8.03,7.09,14.024,11,13,17(31),18,24,26, were calculated by the B3LYP density functional model using 6-31G, 6-311G, 6-311++G and 6-311++G(d,p) basis sets. B3LYP calculation results indicated some selected bond length and bond angle values for this molecule. The optimized geometries and frequencies of the stationary point and the minimum-energy of this structure were recognized. The obtained results were compared with the corresponding experimental data. Trustworthiness of this results is confirmed by good agreement with the experimental analyzes of this structure. The results obtained by different basis sets were compared and the necessity of correlation methods for studying these systems is discussed.

show abstract

ChemInform Abstract: Efficient Synthesis of (.+‐.)‐Horsfiline Through the MgI₂‐Catalyzed Ring‐Expansion Reaction of a Spiro[cyclopropane‐1,3′‐indol]‐2′‐one.

Cited by 7 publications

References 1 publication

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

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

Computational Studies and Energies for the Dioxa-Pentaazaheptacyclo-Hentriaconta-Octaen-One through Density Functional Theory and Natural Bond Orbital

Contact Info

Product

Resources

About

ChemInform Abstract: Efficient Synthesis of (.+‐.)‐Horsfiline Through the MgI2‐Catalyzed Ring‐Expansion Reaction of a Spiro[cyclopropane‐1,3′‐indol]‐2′‐one.

Cited by 7 publications

References 1 publication

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

Recent Advances in Stereoselective Ring Expansion of Spirocyclopropanes: Access to the Spirocyclic Compounds

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

Computational Studies and Energies for the Dioxa-Pentaazaheptacyclo-Hentriaconta-Octaen-One through Density Functional Theory and Natural Bond Orbital

Contact Info

Product

Resources

About

ChemInform Abstract: Efficient Synthesis of (.+‐.)‐Horsfiline Through the MgI₂‐Catalyzed Ring‐Expansion Reaction of a Spiro[cyclopropane‐1,3′‐indol]‐2′‐one.