Asymmetric synthesis catalyzed by chiral ferrocenylphosphine - transition-metal complexes. 8. Palladium-catalyzed asymmetric allylic amination

Hayashi, Tamio; Yamamoto, Akihiro; Ito, Yoshihiko; Nishioka, Eriko; Miura, Hitoshi; Yanagi, Kazunori

doi:10.1021/ja00198a048

Cited by 353 publications

(141 citation statements)

References 2 publications

(6 reference statements)

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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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“…The two cyclopentadienyl rings are planar, parallel and eclipsed. The range of the Fe to cyclopentadienyl C-atom distances [1.97 (4)-2.09 (5) ,~,] is similar to that for other ferrocenes (Hayashi, Yamamoto, Ito, Nishioka, Miura & Yanagi, 1989), but the two bridgehead C atoms are not symmetrically bonded to the Fe atom. The ansa bridge is slightly distorted with the central C atom nearest to being sp 3 hybridized.…”

Section: Commentmentioning

confidence: 67%

Chloro[(α-dimethylamino[3]ferrocenophan-2-yl)diphenylphosphino]gold(I) Benzene Solvate

Viotte¹,

Gautheron²,

Parish³

et al. 1996

Acta Crystallogr C

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“…A transition metal-catalyzed asymmetric allylic amination is one of the most useful methods for synthesizing chiral allylic amines. 92) Several transition metal-catalyzed asymmetric allylic aminations using Pd, [93][94][95][96][97][98][99] Ir, 100) or other transition metal catalysts 101,102) have been reported. The success of the asymmetric allylic substitution reactions with carbon nucleophiles led us to examine asymmetric allylic amination using the Pd-DIAPHOX catalyst system.…”

Section: Pd-catalyzed Asymmetric Allylic Substitution Reactions Usingmentioning

confidence: 99%

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

Nemoto

2008

CHEMICAL & PHARMACEUTICAL BULLETIN

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This review describes the development of a new class of chiral phosphorus ligands: amino acid-derived Pchirogenic diaminophosphine oxides, DIAPHOXs, and their application to several transition metal-catalyzed asymmetric allylic substitution reactions. Pd-catalyzed asymmetric allylic alkylation with cyclic b b-keto esters as prochiral nucleophiles was initially examined using P-chirogenic diaminophosphine oxide 1a, resulting in highly enantioselective construction of quaternary stereocenters. Mechanistic investigations revealed that 1a is activated by N,O-bis(trimethylsilyl)acetamide-induced tautomerization to afford a trivalent diamidophosphite species 13, which functions as the actual ligand. Pd-catalyzed asymmetric allylic substitutions of both acyclic and cyclic substrates were also examined using various nucleophiles such as malonate derivatives, nitromethane, aliphatic amines, and aromatic amines, providing a variety of chiral compounds with good to excellent enantioselectivity. In addition, Ir-catalyzed asymmetric allylic amination and alkylation of terminal allylic carbonates were examined using structurally optimized P-chirogenic diaminophosphine oxides, and the corresponding branched products were obtained in a highly regio-and enantioselective manner. Furthermore, the developed catalytic asymmetric process was successfully applied to the catalytic enantioselective synthesis of biologically active compounds, (R)-preclamol, (R)-baclofen hydrochloride, and (؊)-paroxetine.

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Asymmetric synthesis catalyzed by chiral ferrocenylphosphine - transition-metal complexes. 8. Palladium-catalyzed asymmetric allylic amination

Cited by 353 publications

References 2 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

Chloro[(α-dimethylamino[3]ferrocenophan-2-yl)diphenylphosphino]gold(I) Benzene Solvate

Transition Metal-Catalyzed Asymmetric Reactions Using P-Chirogenic Diaminophosphine Oxides: DIAPHOXs

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