Regio‐ and Stereoselective Rhodium‐Catalyzed Allylic Alkylations of Chelated Enolates

Kazmaier, Uli; Stolz, Daniel

doi:10.1002/anie.200600100

Cited by 78 publications

(26 citation statements)

References 38 publications

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“…Kazmaier and Stolz used chelated amino acid ester enolates as nonsymmetric nucleophiles [271] . γ , δ -Unsaturated amino acids were formed with good diastereoselectivity in the presence of the Wilkinson catalyst.…”

Section: Fundamentals Of R H -Catalyzed Allylic Alkylationsmentioning

confidence: 99%

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Asymmetric CarbonCarbon Bond‐Forming Reactions

Chan

Helmchen

et al. 2010

Catalytic Asymmetric Synthesis

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The catalytic asymmetric conjugate addition to α , β -unsaturated compounds is one of the most powerful carbon -carbon and carbon -heteroatom bond -forming reactions in organic synthesis. The reaction is enormously useful for the construction of enantioenriched, highly functionalized carbon skeletons for the total syntheses of numerous biologically active compounds. The scope of the reaction is broad, owing to the availability of a large variety of donor and acceptor compounds. The high potential of this synthetic method is evident with the possibility of building multiple stereocenters in a single synthetic operation, and many asymmetric catalytic systems can exhibit high reactivity and stereoselectivity. In this chapter, recent advances in catalytic asymmetric conjugate addition reactions are described according to four categories: (i) conjugate addition of organometallics, (ii) conjugate addition of other carbon -centered nucleophiles, (iii) tandem conjugate addition reactions, and (iv) conjugate addition of heteroatom nucleophiles. 8A.2. CATALYTIC ASYMMETRIC CONJUGATE ADDITION OF ORGANOMETALLICSThe catalytic asymmetric conjugate addition of organometallic reagents to electrophilically activated olefi ns constitutes one of the most powerful methods for carbon -carbon Catalytic Asymmetric Synthesis, Third Edition, Edited by Iwao Ojima

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Section: Fundamentals Of R H -Catalyzed Allylic Alkylationsmentioning

confidence: 99%

“…This problem could be solved by Kazmaier and Stolz using chelated ester enolates [271] . The unsaturated amino acids obtained are confi gurationally stable, and as a result of chelation, excellent diastereoselectivities are obtained.…”

Section: B6111 Substrate -Controlled Asymmetric Allylic Alkylatmentioning

confidence: 99%

Asymmetric CarbonCarbon Bond‐Forming Reactions

Chan

Helmchen

et al. 2010

Catalytic Asymmetric Synthesis

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“…25 It has been found that the Rh-catalysed allylic de alkylation is as efficient and versatile as the Pd-catalysed version. In reactions of chelated enolates with suitable protecting groups, high yields and selectivities were obtained, and the regioselectivity can be directed by the reaction parameters.…”

Section: Eementioning

confidence: 99%

“…The synthesis of a new enantiopure, conformationally constrained 1,4-amino alcohol (25) has been reported, starting from commercially available reagents from the chiral pool. 107 This 1,4-amino alcohol has been used as a chiral ligand in the addition of ee Et 2 Zn to aldehydes (best ee 98%) and in the synthesis of chiral propargylic alcohols (best ee 70%) by alkynylzinc species.…”

Section: Phmentioning

confidence: 99%

Carbanions and Electrophilic Aliphatic Substitution

Birsa

2010

Organic Reaction Mechanisms · 2006

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“…[14] An alternative approach to the same type of unsaturated amino acids is based on transition-metal catalyzed allylic alkylation reaction either of glycine-derived Schiff bases [15] or of the chelated enolates already mentioned (Scheme 1). [16] Besides the commonly used Pd-catalysts, other metals such as Ir, [17] Rh, [18] and…”

Section: Introductionmentioning

confidence: 99%

Palladium‐Catalyzed Allylic Alkylation Reactions of Glycolates as a Tool for the Synthesis of Functionalized α‐Hydroxy Esters

2015

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In the design of anticancer gold(I) complexes with high in vivo efficacy, tuning the thiol reactivity to achieve stability towards blood thiols yet maintaining the thiol reactivity to target cellular thioredoxin reductase (TrxR) is of pivotal importance. Herein we describe a dinuclear gold(I) complex (1‐PF6) utilizing a bridging bis(N‐heterocyclic carbene) ligand to attain thiol stability and a diphosphine ligand to keep appropriate thiol reactivity. Complex 1‐PF6 displays a favorable stability that allows it to inhibit TrxR activity without being attacked by blood thiols. In vivo studies reveal that 1‐PF6 significantly inhibits tumor growth in mice bearing HeLa xenograft and mice bearing highly aggressive mouse B16‐F10 melanoma. It inhibits angiogenesis in tumor models and inhibits sphere formation of cancer stem cells in vitro. Toxicology studies indicate that 1‐PF6 does not show systemic anaphylaxis on guinea pigs and localized irritation on rabbits.

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Regio‐ and Stereoselective Rhodium‐Catalyzed Allylic Alkylations of Chelated Enolates

Cited by 78 publications

References 38 publications

Asymmetric CarbonCarbon Bond‐Forming Reactions

Asymmetric CarbonCarbon Bond‐Forming Reactions

Carbanions and Electrophilic Aliphatic Substitution

Palladium‐Catalyzed Allylic Alkylation Reactions of Glycolates as a Tool for the Synthesis of Functionalized α‐Hydroxy Esters

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