Enantioselective Copper-Catalyzed SN2′ Substitution with Grignard Reagents

Alexakis, Alexandre; Malan, Christophe; Lea, Louise; Benhaim, Cyril; Fournioux, Xavier

doi:10.1055/s-2001-14626

Cited by 96 publications

(36 citation statements)

References 23 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Nach ersten Untersuchungen zu Cu-katalysierten allylischen Substitutionen von Cinnamylchlorid mit GrignardReagentien [262,263] wurde diese Umwandlung mit Phosphoramiditen als chiralen Liganden optimiert (Schema 48). [264,265] Dabei waren die ortho-Methoxysubstituenten in dem Binaphthol-Phosphoramidit-Liganden L28 entscheidend für eine hohe Selektivität.…”

Section: Kupferkatalysierte Allylische Substitutionen Mit Grignardreaunclassified

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

2010

View full text Add to dashboard Cite

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.

show abstract

Section: Kupferkatalysierte Allylische Substitutionen Mit Grignardreaunclassified

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

2010

View full text Add to dashboard Cite

show abstract

“…In the accompanying paper Alexakis et al 22 disloses a chiral phosphorous ligand for the Cu-catalyzed S N 2' substitution of cinnamyl chlorides by Grignard reagents.…”

Section: Methodsmentioning

confidence: 99%

Ferrocenyl Thiolates as Ligands in the Enantioselective Copper-Catalyzed Substitution of Allylic Acetates with Grignard Reagents

Karlström¹,

Huerta²,

Meuzelaar³

et al. 2001

Synlett

View full text Add to dashboard Cite

Abstract:The application of ferrocenyl thiolates as ligands in copper-catalyzed asymmetric substitution reactions of allylic acetates with Grignard reagents is reported. The catalyst formed from lithium thiolate 12 gave the γ-products in high selectivity and with up to 64% ee.Keywords: asymmetric synthesis, copper, ferrocenyl ligands, sulfur, asymmetric catalysis Chiral ferrocenes have received much attention as ligands in transition-metal-catalyzed asymmetric reactions.

show abstract

“…Knochel's work [15] illustrated that bulky dialkylzinc reagents were also suitable nucleophiles. In 2001, our group [16] and the Alexakis group [17] used phosphoramidites in combination with linear dialkylzinc and Grignard nucleophiles, respectively. Modular peptide-based ligands developed by Hoveyda et al [18,19] provide highly effective catalysts for a number of different substrates using organozinc compounds; these methods also provide access to quaternary centers.…”

Section: Overviewmentioning

confidence: 99%

Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

Geurts

Fletcher

Zijl

et al. 2008

Pure and Applied Chemistry

View full text Add to dashboard Cite

Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents Geurts, Koen; Fletcher, Stephen P.; van Zijl, Anthoni W.; Minnaard, Adriaan J.; Feringa, Ben L.; Bignall, H. E.; Jauncey, D. L.; Lovell, J. E. J.; Tzioumis, A. K.; Kedziora-Chudczer, L. L. Abstract: Asymmetric allylic alkylations (AAAs) are among the most powerful C-C bondforming reactions. We present a brief overview of copper-catalyzed AAAs with organometallic reagents and discuss our own contributions to this field. Work with zinc reagents and phosphoramidite ligands provided a framework for later developments which employ Grignard reagents and ferrocenyl ligands. High yields and excellent regioselectivities and enantioselectivities are achieved. The AAAs may be more general than previously envisioned, in terms of using substrates functionalized with heteroatoms at various positions; heteroatom substituents at the γ-position provide densely functionalized building blocks. These h-AAA reactions rely on the design of appropriate substrates containing heteroatoms and have allowed us to demonstrate viable new approaches toward the synthesis of versatile organic building blocks. We illustrate that the chiral secondary allylic alcohols, primary homoallylic alcohols and amines can readily be obtained in high enantiomeric purity in a catalytic asymmetric fashion by copper-catalyzed AAAs. Furthermore, we show that manipulation of the terminal olefin provides chiral building blocks where the ee of the starting materials is preserved.

show abstract

Enantioselective Copper-Catalyzed SN2′ Substitution with Grignard Reagents

Abstract: Cinnamyl chlorides undergo selective S N 2' allylic substitution by Grignard reagents using catalytic amount (1 mol%) of CuCN and 1-2 mol% trivalent phosphorus ligand, in dichloromethane. With chiral phosphorus ligands derived from TADDOL ee's up to 73% could be obtained.

Cited by 96 publications

References 23 publications

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

Phosphoramidite: privilegierte Liganden in der asymmetrischen Katalyse

Ferrocenyl Thiolates as Ligands in the Enantioselective Copper-Catalyzed Substitution of Allylic Acetates with Grignard Reagents

Copper-catalyzed asymmetric allylic substitution reactions with organozinc and Grignard reagents

Contact Info

Product

Resources

About