Construction of Spiro[pyrrolidine‐3,3′‐oxindoles] — Recent Applications to the Synthesis of Oxindole Alkaloids

Marti, Christiane; Carreira, Erick M.

doi:10.1002/chin.200337218

Cited by 14 publications

(13 citation statements)

References 1 publication

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“…The face selective oxygenation of C2/C3-fused indoles is a well-established route to hydroxyindolenines, which serve as precursors to the corresponding spirooxindoles 23 . As such, we envisioned the oxygenation of indole 25 (Figure 4A) as a path to the spirooxindole structural moiety found in 1 , 2 , 4 and 6 .…”

Section: Resultsmentioning

confidence: 99%

Total synthesis and isolation of citrinalin and cyclopiamine congeners

Mercado-Marin

García-Reynaga

Romminger

et al. 2014

Nature

151

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It is said that carbon, the most abundant element in organic matter, supplies life’s quantity, whereas nitrogen supplies its quality. It is therefore unsurprising that many natural products that contain basic nitrogens (alkaloids) are coveted for their benefit to human health. However, nitrogen is known to mire many chemical syntheses because of its basicity and susceptibility to oxidation. This challenge may be heightened by the presence of more than one nitrogen atom in a targeted complex alkaloid, but can be met by the selective introduction and removal of functional groups that mitigate basicity, as highlighted herein with the first chemical syntheses of citrinalin B and cyclopiamine B. The chemical connections that have been realized as a result of these syntheses, in addition to the isolation of both 17-hydroxycitrinalin B and citrinalin C through 13C feeding studies, supports the existence of a common bicyclo[2.2.2]diazaoctane containing biogenetic precursor to these compounds as has been proposed previously.

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Section: Resultsmentioning

confidence: 99%

Total synthesis and isolation of citrinalin and cyclopiamine congeners

Mercado-Marin

García-Reynaga

Romminger

et al. 2014

Nature

151

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“…Spiroindoles possessing a stereogenic center at C-3 [15,16] and thiazolidine derivatives have also wide applications in synthetic and medicinal chemistry [17][18][19][20][21]. In view of the above mentioned findings and as continuation of our efforts in the synthesis of new biologically active heterocycles [22,23].…”

Section: Introductionmentioning

confidence: 98%

Synthesis and antimicrobial activity of some novel 2-thienyl substituted heterocycles

Youssef

Abeed

2014

Heterocyclic Communications

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“…The 3,3′-pyrrolidinyl-spirooxindole scaffold has been the subject of many elegant asymmetric syntheses, 16 which usually involve multistep diastereoselective transformations using chiral auxiliaries. The pyrrolidinyl moiety embedded in the spirooxindole may be built up through a highly versatile [3 + 2] cycloaddition strategy.…”

Section: Introductionmentioning

confidence: 99%

Catalytic Enantioselective 1,3-Dipolar Cycloadditions of Azomethine Ylides for Biology-Oriented Synthesis

et al. 2014

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ConspectusCycloaddition reactions are among the most powerful methods for the synthesis of complex compounds. In particular, the development and application of the 1,3-dipolar cycloaddition, an important member of this reaction class, has grown immensely due to its powerful ability to efficiently build various five-membered heterocycles. Azomethine ylides are commonly used as dipoles for the synthesis of the pyrrolidine scaffold, which is an important motif in natural products, pharmaceuticals, and biological probes. The reaction between azomethine ylides and cyclic dipolarophiles allows access to polycyclic products with considerable complexity. The extensive application of the 1,3-dipolar cycloaddition is based on the fact that the desired products can be obtained with high yield in a regio- and stereocontrolled manner. The most attractive feature of the 1,3-dipolar cycloaddition of azomethine ylides is the possibility to generate pyrrolidines with multiple stereocenters in a single step. The development of enantioselective cycloadditions became a subject of intensive and impressive studies in recent years. Among many modes of stereoinduction, the application of chiral metal–ligand complexes has emerged as the most viable option for control of enantioselectivity.In chemical biology research based on the principle of biology-oriented synthesis (BIOS), compound collections are prepared inspired by natural product scaffolds. In BIOS, biological relevance is employed as the key criterion to generate hypotheses for the design and synthesis of focused compound libraries. In particular, the underlying scaffolds of natural product classes provide inspiration for BIOS because they define the areas of chemical space explored by nature, and therefore, they can be regarded as “privileged”. The scaffolds of natural products are frequently complex and rich in stereocenters, which necessitates the development of efficient enantioselective methodologies.This Account highlights examples, mostly from our work, of the application of 1,3-dipolar cycloaddition reactions of azomethine ylides for the catalytic enantioselective synthesis of complex products. We successfully applied the 1,3-dipolar cycloaddition in the synthesis of spiro-compounds such as spirooxindoles, for kinetic resolution of racemic compounds in the synthesis of an iridoid inspired compound collection and in the synthesis of a nitrogen-bridged bicyclic tropane scaffold by application of 1,3-fused azomethine ylides. Furthermore, we performed the synthesis of complex molecules with eight stereocenters using tandem cycloadditions. In a programmable sequential double cycloaddition, we demonstrated the synthesis of both enantiomers of complex products by simple changes in the order of addition of chemicals. Complex products were obtained using enantioselective higher order [6 + 3] cycloaddition of azomethine ylides with fulvenes followed by Diels–Alder reaction. The bioactivity of these compound collections is also discussed.

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Construction of Spiro[pyrrolidine‐3,3′‐oxindoles] — Recent Applications to the Synthesis of Oxindole Alkaloids

Abstract: For Abstract see ChemInform Abstract in Full Text.

Cited by 14 publications

References 1 publication

Total synthesis and isolation of citrinalin and cyclopiamine congeners

Total synthesis and isolation of citrinalin and cyclopiamine congeners

Synthesis and antimicrobial activity of some novel 2-thienyl substituted heterocycles

Catalytic Enantioselective 1,3-Dipolar Cycloadditions of Azomethine Ylides for Biology-Oriented Synthesis

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