Palladium‐Catalyzed Asymmetric Allylic Alkylation of 3‐Aryloxindoles with Allylidene Dipivalate: A Useful Enol Pivalate Product

Trost, Barry M.; Masters, James T.; Burns, Aaron C.

doi:10.1002/anie.201209783

Cited by 47 publications

(12 citation statements)

References 52 publications

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“…Following our initial success in the asymmetric prenylation of 3‐alkyloxindoles, we decided to investigate whether regiocontrol and enantiocontrol could also be achieved with 3‐aryloxindoles as nucleophiles. Excellent results with this class of nucleophiles have previously been achieved by our group in the Pd‐catalyzed asymmetric alkylation, the Mo‐catalyzed enantio‐ and diastereoselective allylation with cinnamyl and related carbonates, the Pd‐catalyzed enantio‐ and diastereoselective allylation with benzyloxyallenes, the Pd‐catalyzed asymmetric benzylation, and the Pd‐catalyzed asymmetric allylation with allylidene dipivalate …”

Section: Resultsmentioning

confidence: 81%

Development of the Regiodivergent Asymmetric Prenylation of 3‐Substituted Oxindoles

Trost

Chan

Malhotra

2017

Chemistry A European J

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This paper fully describes our efforts to design a Pd-catalyzed asymmetric prenylation of 3-substituted oxindoles that affords access to both the linear and reverse-prenylated products. Both 3-alkyl- and 3-aryloxindoles performed well under our optimized reaction conditions. The regiodivergent alkylation of monoterpene-derived electrophiles using this methodology was also investigated. The utility of this methodology in natural product synthesis was demonstrated through the efficient total syntheses of four Flustra alkaloids, which also allowed the absolute stereochemistry of the prenylated oxindole products to be assigned. Surprisingly, the same enantiomer of ligand produced linear and branched regioisomers of opposite chirality.

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Section: Resultsmentioning

confidence: 81%

Development of the Regiodivergent Asymmetric Prenylation of 3‐Substituted Oxindoles

Trost

Chan

Malhotra

2017

Chemistry A European J

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“…The 3,3‐disubstituted oxindole motif, in particular, has attracted considerable attention, as it occurs in a variety of biologically and pharmacologically active compounds . Most published enantioselective syntheses employ noble metals, whereas 3d transition‐metal‐catalyzed as well as organocatalytic methods have been recently introduced.…”

Section: Figurementioning

confidence: 99%

Radical Changes in Lewis Acid Catalysis: Matching Metal and Substrate

et al. 2016

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Whereas the stereochemical rigidity of the coordination sphere of boxmi/Cu II catalysts is key to achieving high enantioselectivity in the electrophilic alkylation of b-ketoesters, this pathway is outperformed by ar adical process for the corresponding catalytic transformation of oxindoles,g iving rise to racemic products.F or the corresponding Zn II catalysts, the selectivity in the latter process is outstanding despite the greater plasticity of the coordination shell. This reaction was thus developed into ah ighly useful synthetic method, which enabled the conversion of wide range of substrates with high yields and enantioselectivities.

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“…Geminal-dicarboxylates are an understudied class of compounds with the exception of the diacetate and dipropionate derivatives, which can protect aldehydes and are important substrates for asymmetric Tsuji–Trost reactions. 50 , 51 …”

Section: Introductionmentioning

confidence: 99%