Enantioselective Synthesis of 3,3-Disubstituted Oxindoles through Pd-Catalyzed Cyanoamidation

Yasui, Yoshizumi; Kamisaki, Haruhi; Takemoto, Yoshiji

doi:10.1021/ol801168j

Cited by 180 publications

(71 citation statements)

References 37 publications

(35 reference statements)

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“…[459] Das Cyano- Die erste erfolgreiche Anwendung eines PhosphoramiditSilberkomplexes wurde ebenfalls erst kürzlich beschrieben. [460] Dabei wurden durch silberkatalysierte 1,3-dipolare Cycloaddition der arylsubstituierten Iminoglycinate 338 mit aktivierten Alkenen wie tert-Butylacrylat (339) [461] die Prolinderivate 340 erhalten.…”

Section: Palladiumkatalysierte Cyanoamidierungunclassified

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

2010

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Die asymmetrische Katalyse mit Übergangsmetallkomplexen ist die Grundlage unzähliger stereoselektiver Umwandlungen und hat damit das Bild der modernen Synthesechemie gewandelt. Der Schlüssel zum Erfolg war die Entwicklung chiraler Liganden zur Kontrolle der Regio‐, Diastereo‐ und Enantioselektivität. Dabei haben sich Phosphoramidite als eine äußerst vielseitige und leicht zugängliche Klasse von chiralen Liganden erwiesen. Ihre modulare Struktur ermöglicht die Herstellung von Ligandenbibliotheken und erleichtert die Feinabstimmung für eine bestimmte katalytische Reaktion. Phosphoramidite bewirken oft außerordentlich hohe Stereoselektivitäten, und ihre einzähnige Natur ist in der kombinatorischen Katalyse, die gemischte Liganden verwendet, unverzichtbar. In diesem Aufsatz werden neue Entwicklungen in der asymmetrischen Katalyse mit Phosphoramiditen diskutiert, wobei der Schwerpunkt auf der Bildung von Kohlenstoff‐ Kohlenstoff‐ und Kohlenstoff‐Heteroatom‐Bindungen liegt.

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Section: Palladiumkatalysierte Cyanoamidierungunclassified

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

2010

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“…2 烯丙基取代的氰醇化合物以及 α-胺基腈在非金属催化的分子内碳氰化反应中的应用过渡金属催化的烯烃及炔烃的分子内氰官能团化反应是一类重要的碳碳键形成反应, 也是制备官能团化腈类化合物最有效和便捷的方法之一 [15] . 该类反应通 …”

Section: α-胺基腈与unclassified

Lewis Base-Catalyzed Allylic Alkylation ofα-Amino Nitriles and Cyanohydrins and Synthetic Applications

秦天游¹,

张晓安

寮渭巍³

2014

Chin. J. Org. Chem.

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This article summarized our recent progress in Lewis base-catalyzed the direct allylic substitutions of Morita-Baylis-Hillman (MBH) adducts with α-amino nitriles and cyanohydrins bearing an α-hydrogen, which provided efficient access to functionalized α-amino nitriles and cyanohydrins incorporating quaternary carbon centers. On the basis of these, a novel metal-free carbocyanation (alkenylcyanation and acylcyanation) approach to construct functionalized nitriles incorporating β-quaternary carbon center has been developed. In addition, the several factors influencing these chemical transformations are discussed, and the possible mechanism is proposed.

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“…Phosphoramidites L9, 37 L11, 38 L12, 39 and L13 40 derived from dimethyl BINOL, biphenol, spirobiindane diol, and TADDOL, respectively, unexpectedly resulted in higher reactivity than L8 but poorer selectivity (entries 9, 11-13). Bisphosphorus ligands L14, L15, 41 and L16 42 gave poor conversion and selectivity (entries [14][15][16]. The effects of solvents and additives were examined with using 2 mol % Pd(dba) 2 and 8 mol % phosphoramidite L8 (Table 5).…”

Section: Enantioselective Synthesis Of 33-disubstituted Oxindolesmentioning

confidence: 99%

“…15 Replacement of the alkyne with an alkene led to the formation of a,a-disubstituted lactams: a palladium-catalyzed Heck-type reaction proceeded from alkenyl chloroformamides to give a-vinyl lactams. 16 As part of these studies, the reaction of alkenyl cyanoformamides with palladium catalyst was found to give a-cyanomethyl lactams. This reaction was applied to the synthesis of 3,3-disubstituted oxindoles and other a,a-disubstituted lactams and was expanded to enantioselective transformation.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of 3,3-disubstituted oxindoles through Pd-catalyzed intramolecular cyanoamidation

et al. 2010

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a b s t r a c tThe cyanoamidation of olefins was achieved. When N-(2-vinylphenyl)cyanoformamides were treated with palladium catalyst, intramolecular cyanoamidation took place to give corresponding 3,3-disubstituted oxindoles. P(t-Bu) 3 showed a remarkable effect on this reaction. When it was used with Pd(dba) 2 , the reaction was completed in 15 min at 100 C for many substrates. Furthermore, the enantioselective cyanoamidation was accomplished with Pd(dba) 2 and an optically active phosphoramidite to provide optically active 3,3-disubstituted oxindoles. Manipulation of the resulting oxindoles has been studied.

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Enantioselective Synthesis of 3,3-Disubstituted Oxindoles through Pd-Catalyzed Cyanoamidation

Abstract: The first enantioselective cyanoamidation of olefins provides quick access to a variety of 3,3-disubstituted oxindoles. The combination of Pd(dba)2, an optically active phosphoramidite, and N, N-dimethylpropylene urea (DMPU) in decalin were found to be the best conditions.

Cited by 180 publications

References 37 publications

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

Lewis Base-Catalyzed Allylic Alkylation ofα-Amino Nitriles and Cyanohydrins and Synthetic Applications

Synthesis of 3,3-disubstituted oxindoles through Pd-catalyzed intramolecular cyanoamidation

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