Chiral arenethiolatocopper(I) catalyzed substitution reactions of acyclic allylic substrates with Grignard reagents

Klaveren, M. van; Persson, E. S. M.; Villar, Amaya del; Grove, David M.; Bäckvall, Jan‐E.; Koten, Gerard van

doi:10.1016/0040-4039(95)00426-d

Cited by 134 publications

(45 citation statements)

References 23 publications

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“…18,19 Mixing of 12 and CuI in Et 2 O or toluene at room temperature led to a clear yellow solution within 30 min. Addition of allylic ester 9 or 14 to this solution, followed by n-BuMgI, according to our previously reported S N 2'-selective reaction conditions, 15,16 gave the desired γ-substitution products 10, together with small amounts of α-substitution product 15 (eq 2, Table 1). …”

Section: Methodsmentioning

confidence: 94%

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

Karlström¹,

Huerta²,

Meuzelaar³

et al. 2001

Synlett

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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.

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Section: Methodsmentioning

confidence: 94%

“…15 The use of copper arenethiolates prepared in situ from the corresponding arenethiols has also been studied for the asymmetric version of this reaction. 16 Similar results were obtained as when preformed copper arenethiolates were used.…”

mentioning

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

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“…1. The groups of Bäckvall and van Koten [13] were the first to report AAAs in 1995 using Grignard reagents and allylic acetates (42 % ee) later [14] improved upon by using the ferrocenyl ligands shown in Fig. 1.…”

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

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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.

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“…59 The first report on the catalytic version is due to Backvall and van Koten, in 1995. 60 They used a Grignard reagent as primary organometallics, and a copper thiolate as chiral catalyst (15% is not yet very large as the substrate is concerned. Knochel's procedure is better for hindered dialkylzincs (ee's up to >95%), whereas Hoveyda's one allow for the efficient reaction with trisubstituted allylic phosphates.…”

Section: Scheme 11mentioning

confidence: 99%

Asymmetric Organocopper Chemistry: Cu-Catalyzed Conjugate Addition and Allylic Substitution

Alexakis

2004

ACS Symposium Series

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This review deals with the most recent developments in the asymmetric conjugate addition and allylic substitution. For the conjugate addition, the best enantioselectivities (>99%) have been attained with dialkylzinc reagents and 0.5-2% CuX and 1-4% of a chiral trivalent phosphorus ligand. The γ-allylic substitution can be achieved equally well with, either dialkylzinc or Grignard reagents, and the same catalysts.Oragnocopper chemistry is a standard synthetic tool nowadays.1 There are thousands of natural products, which have been synthesized using this chemistry, at least in one step. The most popular reactions are 1) the conjugate addition, 2) the substitution, and particularly the allylic substitution, 3) the cleavage of epoxides, and 4) the carbocupration.

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Chiral arenethiolatocopper(I) catalyzed substitution reactions of acyclic allylic substrates with Grignard reagents

Cited by 134 publications

References 23 publications

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

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

Asymmetric Organocopper Chemistry: Cu-Catalyzed Conjugate Addition and Allylic Substitution

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