Direct Asymmetric α-Allylation of α-Branched Aldehydes by Two Catalytic Systems with an Achiral Pd Complex and a Chiral Primary α-Amino Acid

Yoshida, Masanori; Terumine, Tatsuaki; Masaki, Erika; Hara, Shoji

doi:10.1021/jo4018414

Cited by 57 publications

(20 citation statements)

References 58 publications

(19 reference statements)

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“…However, noticeably absent is the use of protected α‐amino‐ and α‐hydroxy‐ acetaldehydes 5. There are merely four reactions reported to date, which involve Pd‐catalyzed allylation to afford γ,δ‐unsaturated adducts in racemic form5a,b or at best 46 % ee 5c. The use of a suitably protected α‐aminoacetaldehyde in a dual catalytic process of the type shown in Scheme could result in a fully stereodivergent synthesis of β,β′‐disubstituted α‐amino acid derivatives.…”

Section: Methodsmentioning

confidence: 99%

Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes

et al. 2015

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Fully stereodivergent dual-catalytic α-allylation of protected α-amino- and α-hydroxyacetaldehydes is achieved through iridium- and amine-catalyzed substitution of racemic allylic alcohols with chiral enamines generated in situ. The operationally simple method furnishes useful aldehyde building blocks in good yields, more than 99% ee, and with d.r. values greater than 20:1 in some cases. Additionally, the γ,δ-unsaturated products can be further functionalized in a stereodivergent fashion with high selectivity and with preservation of stereochemical integrity at the Cα position.

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Section: Methodsmentioning

confidence: 99%

Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes

et al. 2015

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“…123 A related allylation of α,α -disubstituted aldehydes was developed by Yoshida, which involves capture of the π-allylpalladium intermediate by an enamine derived from a chiral α-stereogenic amino acid. 124, 125 Most recently, Stoltz and Marek reported decarboxylative Tsuji-Trost allylations of fully-substituted amide enolates to form acyclic quaternary carbon stereocenters. 126 Remote electronic effects of the phosphine ligand XXXVII were required to enforce optimal levels of enantioselectivity.…”

Section: Acyclic Quaternary Carbon Stereocentersmentioning

confidence: 99%

Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

2017

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Whereas numerous asymmetric methods for formation of quaternary carbon stereocenters in cyclic systems have been documented, the construction of acyclic quaternary carbon stereocenters with control of absolute stereochemistry remains a formidable challenge. This review summarizes enantioselective methods for the construction of acyclic quaternary carbon stereocenters from achiral or chiral racemic reactants via transition metal catalysis.

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“…Soon after, Yoshida and co-workers reported a similar reaction catalyzed by chiral amino acids and palladium. 12 Finally, Zhang et al reported the α-allylation of branched aldehydes by using pyrrolidine and chiral palladium(II) complexes. 13 In both examples, the branched aldehydes were obtained in good yields and with excellent enantioselectivities, albeit in low diastereoselectivities in Zhang's case.…”

Section: Scheme 5 Enantioselective Version Of the Allylation Of Lineamentioning

confidence: 99%

Merging Transition-Metal Activation and Aminocatalysis

Meazza

Rios

2016

Synthesis

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In this review the principal enantioselective methodologies merging transition-metal catalysis and aminocatalysis are disclosed. 1 Introduction 2 Transition-Metal and Enamine Catalysis 3 Transition-Metal and Iminium Catalysis 4 Transition-Metal Catalysis and Organocascade (Iminium/Enamine) Activation 5 Conclusions and Perspectives Key words synergistic catalysis, multicatalysis, organocatalysis, transition-metal catalysis, cascade reactions Marta Meazza (left) was born in 1987 in Saronno (Italy). She graduated from the University of Milan in 2012 with a Master's degree in chemistry and pharmaceutical technology, under the supervision of Prof. Egle Beccalli. Subsequently, she started her PhD under the supervision of Dr. Ramon Rios at the University of Southampton (UK), studying new asymmetric reactions for the synthesis of azaarenes through synergistic catalysis, combining an organocatalyst and a metal catalyst. She also investigates organocatalytic photoactivation of organic compounds. Her research interests include organocatalysis, organometallic chemistry, and photocatalysis. Ramon Rios (right) obtained his PhD degree from the University of Barcelona in 2000. He has enjoyed several postdoctoral and research positions with Prof.

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Direct Asymmetric α-Allylation of α-Branched Aldehydes by Two Catalytic Systems with an Achiral Pd Complex and a Chiral Primary α-Amino Acid

Cited by 57 publications

References 58 publications

Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes

Stereodivergent Dual Catalytic α‐Allylation of Protected α‐Amino‐ and α‐Hydroxyacetaldehydes

Acyclic Quaternary Carbon Stereocenters via Enantioselective Transition Metal Catalysis

Merging Transition-Metal Activation and Aminocatalysis

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