Catalytic Asymmetric <i>exo′</i>‐Selective [3+2] Cycloaddition for Constructing Stereochemically Diversified Spiro[pyrrolidin‐3,3′‐oxindole]s

Awata, Atsuko; Arai, Takayoshi

doi:10.1002/chem.201201249

Cited by 114 publications

(25 citation statements)

References 65 publications

(10 reference statements)

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“…[14] To further illustrate the versatility of 3-isothiocyanato oxindoles in the synthesis of structurally complex dispirocyclic thiopyrrolidineoxindole derivatives, we subsequently examined the cascade Michael/cyclization process between 3-isothiocyanato oxindoles and 3-methylene-2-oxindoles (Table 3). [15] To our delight, the cascade Michael/cyclization reactions of 3-isothiocyanato oxindoles 1 a-d and 4 a-o occurred smoothly with 1 mol % catalyst VIII in mesitylene at À10 8C, [16] resulting in a wide range of multisubstituted dispirocyclic bioxindole derivatives 5 a-r containing two spiro-quaternary and three contiguous stereocenters in excellent yields (up to 99 %) and with excellent diastereo-(up to > 99:1 d.r.) and enantioselectivities (up to > 99 % ee; Table 3).…”

Section: T[min]mentioning

confidence: 99%

“…[ www.chemeurj.org cellent results (entries 9-10). Similarly, regardless of the electronic nature of R 3 contained in alkylidene azlactones, the desired products 3 l-p were also obtained in excellent yields with excellent diastereo-and enantioselectivities (entries [11][12][13][14][15]. The absolute configuration of the product 3 m was unambiguously determined as (C7R,C9R,C10S) by Xray crystallographic analysis; [13,14] the other products in Table 2 were tentatively assigned by analogy.…”

Section: T[min]mentioning

confidence: 99%

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3‐Isothiocyanato Oxindoles Serving as Powerful and Versatile Precursors to Structurally Diverse Dispirocyclic Thiopyrrolidineoxindoles through a Cascade Michael/Cyclization Process with Amino‐Thiocarbamate Catalysts

Han

et al. 2013

Chemistry A European J

105

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Section: T[min]mentioning

confidence: 99%

Section: T[min]mentioning

confidence: 99%

3‐Isothiocyanato Oxindoles Serving as Powerful and Versatile Precursors to Structurally Diverse Dispirocyclic Thiopyrrolidineoxindoles through a Cascade Michael/Cyclization Process with Amino‐Thiocarbamate Catalysts

Han

et al. 2013

Chemistry A European J

105

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“…23 The reported procedure is rather versatile with a range of substitutions being tolerated to give the corresponding products with high ee.…”

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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“…In fact, silver and copper catalyzed 1,3-DC are very well known and constitute the most reliable, and direct enantioselective methodology to built up to four stereogenic centers of the resulting proline derivatives [6,15,16,17,18], in only one operation step. In addition, they exhibit more versatility and wider scope than the analogous enantioselective organocatalyzed 1,3-dipolar cycloadditions [19,20,21,22,23,24,25]. However, chiral gold complexes [26,27,28] have not so extensively employed and just a very efficient enantioselective cycloaddition of münchnones with electron-deficient alkenes has been described.…”

Section: Introductionmentioning

confidence: 99%

Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions

Nájera

Sansano

2014

Journal of Organometallic Chemistry

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In this account, we describe the experience of our research group in the implementation of chiral coinage metal complexes into the efficient enantioselective 1,3-DC of azomethine ylides derived from α-amino acids and azlactones with different dipolarophiles. The corresponding chiral metallodipoles were generated in situ and next focused on the synthesis of highly substituted prolines. For this purpose, privileged ligands such as phosphoramidites and binap with silver(I), gold(I) and copper(II) salts are described. Depending from the ligand and mainly from the metal salt it can be possible to control the facial endo/exo-diasteroselectivity and the enantioselectivity of these types of processes. The synthetic processes are also supported by DFT calculations in order to elucidate the most plausible mechanism and the stereochemical results.

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Catalytic Asymmetric exo′‐Selective [3+2] Cycloaddition for Constructing Stereochemically Diversified Spiro[pyrrolidin‐3,3′‐oxindole]s

Cited by 114 publications

References 65 publications

3‐Isothiocyanato Oxindoles Serving as Powerful and Versatile Precursors to Structurally Diverse Dispirocyclic Thiopyrrolidineoxindoles through a Cascade Michael/Cyclization Process with Amino‐Thiocarbamate Catalysts

3‐Isothiocyanato Oxindoles Serving as Powerful and Versatile Precursors to Structurally Diverse Dispirocyclic Thiopyrrolidineoxindoles through a Cascade Michael/Cyclization Process with Amino‐Thiocarbamate Catalysts

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

Coinage metal complexes as chiral catalysts for 1,3-dipolar cycloadditions

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