Allylic alkylation: preparation of .pi.-allylpalladium complexes from olefins

Trost, Barry M.; Strege, Paul E.; Weber, Lothar; Fullerton, Terry J.; Dietsche, Thomas J.

doi:10.1021/ja00479a024

Cited by 162 publications

(98 citation statements)

References 11 publications

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“…[11,27,28] Racemic substrates S1-S7 were prepared as previously reported. [29,30,31,32] [Pd(h [33] [Pd(h [34] and [35] were prepared as previously described. …”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

Mata¹,

Pàmies²,

Diéguez³

2009

Adv Synth Catal

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Abstract:We have screened a library of modular phosphite-oxazoline ligands for asymmetric allylic substitution reactions. The library is efficiently prepared from the commercially available and cheap dglucosamine. The introduction of a phosphite moiety into the ligand design is highly advantageous for the product outcome. Therefore, this ligand library affords good-to-excellent reaction rates [TOFs up to 600 mol substrate (mol Pd h) À1] and enantioselectivities (ees up to 99%) and, at the same time, shows a broad scope for mono-, di-and trisubstituted linear hindered and unhindered substrates and cyclic substrates. The NMR studies on the palladium allyl intermediates provide a deeper understanding about the effect of the ligand parameters on the origin of enantioselectivity.

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“…[11,27,28] Racemic substrates S1-S7 were prepared as previously reported. [29,30,31,32] [Pd(h [33] [Pd(h [34] and [35] were prepared as previously described. …”

Section: Experimental Section General Considerationsmentioning

confidence: 99%

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

Mata¹,

Pàmies²,

Diéguez³

2009

Adv Synth Catal

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“…and [Pd( [40] were prepared as previously deA Preparation of hydroxyl-pyridine (S)-7: Compound 7 was synthesized by a modified previously reported methodology. [15] 2-bromo-6-methylpyridine (4.27 mL, 37.5 mmol) was dissolved in ether (150 mL) and the mixture cooled to À78 8C.…”

Section: Methodsmentioning

confidence: 99%

A New Modular Phosphite‐Pyridine Ligand Library for Asymmetric Pd‐Catalyzed Allylic Substitution Reactions: A Study of the Key Pd‐π‐Allyl Intermediates

Mazuela

Pàmies

Diéguez

2013

Chemistry A European J

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A library of phosphite-pyridine ligands L1-L12 a-g has been successfully applied for the first time in the Pd-catalyzed allylic substitution reactions of several di- and trisubstituted substrates by using a wide range of C, N and O nucleophiles, among which are the little studied α-substituted malonates, β-diketones, and alkyl alcohols. The highly modular nature of this ligand library enables the substituents/configuration at the ligand backbone, and the substituents/configurations at the biaryl phosphite moiety to be easily and systematically varied. We found that the introduction of an enantiopure biaryl phosphite moiety played an essential role in increasing the versatility of the Pd-catalytic systems. Enantioselectivities were therefore high for several hindered and unhindered di- and trisubstituted substrates by using a wide range of C, N and O nucleophiles. Of particular note were the high enantioselectivities (up to>99% ee) and high activities obtained for the trisubstituted substrates S6 and S7, which compare favorably with the best that have been reported in the literature. We have also extended the use of these new catalytic systems in alternative environmentally friendly solvents such as propylene carbonate and ionic liquids. Studies on the Pd-π-allyl intermediates provide a deeper understanding of the effect of ligand parameters on the origin of enantioselectivity.

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“…Elemental analyses were performed by the analytical research services of Ciba-Ceigy AG. Complexes 2b [25] and 2c [4 b] were prepared according to published procedures, 2a was purchased from Johnson-Matthey and recrystallized before use.…”

Section: Experimental Partmentioning

confidence: 99%

Synthesis, Structure, and 2D‐NMR Studies of Novel Chiral (η³‐Allyl)palladium(II) Complexes Containing the Bidentate Ligand Sparteine

Togni

Rihs

Pregosin

et al. 1990

Helvetica Chimica Acta

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Allylic alkylation: preparation of .pi.-allylpalladium complexes from olefins

Cited by 162 publications

References 11 publications

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

A New Modular Phosphite‐Pyridine Ligand Library for Asymmetric Pd‐Catalyzed Allylic Substitution Reactions: A Study of the Key Pd‐π‐Allyl Intermediates

Synthesis, Structure, and 2D‐NMR Studies of Novel Chiral (η³‐Allyl)palladium(II) Complexes Containing the Bidentate Ligand Sparteine

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Allylic alkylation: preparation of .pi.-allylpalladium complexes from olefins

Cited by 162 publications

References 11 publications

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

Pyranoside Phosphite‐Oxazoline Ligand Library: Highly Efficient Modular P,N Ligands for Palladium‐Catalyzed Allylic Substitution Reactions. A Study of the Key Palladium Allyl Intermediates

A New Modular Phosphite‐Pyridine Ligand Library for Asymmetric Pd‐Catalyzed Allylic Substitution Reactions: A Study of the Key Pd‐π‐Allyl Intermediates

Synthesis, Structure, and 2D‐NMR Studies of Novel Chiral (η3‐Allyl)palladium(II) Complexes Containing the Bidentate Ligand Sparteine

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Synthesis, Structure, and 2D‐NMR Studies of Novel Chiral (η³‐Allyl)palladium(II) Complexes Containing the Bidentate Ligand Sparteine