Isatin as a Strategic Motif for Asymmetric Catalysis

Mohammadi, Somayeh; Heiran, Roghayeh; Herrera, Raquel P.; Marqués‐López, Eugenia

doi:10.1002/cctc.201300050

Cited by 95 publications

(40 citation statements)

References 240 publications

(67 reference statements)

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“…[4,5,7] Amongst ketones, much less attention has focused on trifluoromethyl-ketone and isatin (1H-indole-2,3-dione) derivatives. [8][9][10]12,13] In 2007, Shibasaki reported a methodology using a copper salt with Xantphos or phenanthroline as ligand (10 mol%) in the presence of potassium tert-butoxide, allowing the direct alkynylation of trifluoromethyl-ketones in toluene at 100°C (or THF at 60°C) for 12 to 24 h. [9] In parallel, Li described an aqueous process showcasing silver(I)/phosphine as an efficient system for such a transformation. In the latter case, long reactions times (1 to 2 days) were required and the reaction had to be conducted under an inert atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Light‐Stable Silver N‐Heterocyclic Carbene Catalysts for the Alkynylation of Ketones in Air

et al. 2015

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N-Heterocyclic carbene (NHC) silver(I) complexes were efficiently employed in the alkynylation of ketones. These cationic complexes were found highly active and efficient under mild conditions without the need of additive, and in air. The mechanism of this transformation was investigated. Experiments suggest the formation of a silveracetylide key intermediate and the release of one ligand from the silver centre enabling the transformation.

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Section: Introductionmentioning

confidence: 99%

Light‐Stable Silver N‐Heterocyclic Carbene Catalysts for the Alkynylation of Ketones in Air

et al. 2015

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“…22 Previous extensive exploration into the reactivity of isatins (nucleophilic addition to C3 carbonyl, oxidations, spiro-annulations, etc.) has provided useful insights into the potential reactivity of pyrrolidine-2,3-diones, albeit the isatin scaffold bears a fused aromatic ring.…”

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confidence: 99%

Stereoselective Synthesis of Quaternary Pyrrolidine-2,3-diones and β-Amino Acids

Shymanska

Pierce

2017

Org. Lett.

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A facile, diastereoselective synthesis of highly substituted pyrrolidine-2,3-diones is reported, along with the one-step conversion of these heterocycles to novel β-amino acids and further functionalized derivatives. This method involves an unusually mild, one-pot, three-component cyclization/allylation followed by a Claisen rearrangement to provide unusual pyrrolidinone products that are densely functionalized and contain an all-carbon quaternary stereocenter. The reported reaction sequence is operationally simple, exquisitely diastereoselective, and provides gram-scale access to valuable heterocyclic scaffolds and β-amino acids not readily accessible via existing approaches.

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“…As shown in Table 3, the reactions worked very well with isatins bearing either electron-withdrawing or electron-donating substituents on the phenyl ring and the desired productsc an be obtainedi ng ood yields ande nantioselectivities (89-95 % ee)( entry 1, entries [3][4][5][6][7][8][9][10][11][12][13][14][15]. 8b with the substituent at the 4-position retardt he reactive process possibly due to the steric effect, affording the product in 86 % ee (entry 2).…”

Section: Resultsmentioning

confidence: 89%

“…[1] In the last fewy ears,t he asymmetric version of MBH reactionh as been extensively investigated by employings everal different catalytic systems,s uch as cinchonine derivatives and chiral phosphines as well( Figure 1). [2] Among these,t he enantioselective MBH reaction of isatins wasp articularly attractives incet he MBH adducts, [3] 3-substituted 3-hydroxy-2-oxindoles, constitute the core building blocks of many valuable drug candidates. [4][5] In 2010, Zhou and coworkers reported the first MBH reactiono fi satin with acrolein catalyzed by ß-isocupreidine 1a (ß-ICD) providing the oxindole derivatives in excellent enantioselectivity ( Figure 1).…”

Section: Introductionmentioning

confidence: 99%

Tunable Bifunctional Phosphine–Squaramide Promoted Morita–Baylis–Hillman Reaction of N‐Alkyl Isatins with Acrylates

et al. 2015

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As erieso fh ighly tunable bifunctional phosphine-squaramide H-bond donor organocatalysts 6 has been synthesizedf rom inexpensivea nd commercially available b-amino alcohols in moderate yields.C atalyst 6f can efficiently promote the asymmetric Morita-Baylis-Hillman (MBH) reaction of N-alkyl isatins with acrylate estersp roviding the chiral 3-substituted 3-hydroxy-2-oxindoles in good yields and enantioselectivities( up to 93 % yield and9 5% ee), in which the challenging substrate tert-butyl acrylate 9d,p rovided the best ee value to date.M oreover, this methodology was applied successfully in the synthesis of chiral cyclic spiropyrrolizidineoxindolea nd g-butyrolactone derivatives without enantioselectivity deterioration. Thep ossible mechanism of this MBH reactionw as also investigated by 31 PNMR, ESI-MS and KIE studies.T he KIE experiments show that the electrophilic addition of N-methyl isatin to the complexo f acrylate ester and phophine-squaramide is the ratedeterming step of the asymmetric MBH reaction.

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Isatin as a Strategic Motif for Asymmetric Catalysis

Cited by 95 publications

References 240 publications

Light‐Stable Silver N‐Heterocyclic Carbene Catalysts for the Alkynylation of Ketones in Air

Light‐Stable Silver N‐Heterocyclic Carbene Catalysts for the Alkynylation of Ketones in Air

Stereoselective Synthesis of Quaternary Pyrrolidine-2,3-diones and β-Amino Acids

Tunable Bifunctional Phosphine–Squaramide Promoted Morita–Baylis–Hillman Reaction of N‐Alkyl Isatins with Acrylates

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