A Tertiary Phosphine-catalyzed Reaction of Acrylic Compounds with Aldehydes

Morita, Kenichi; Suzuki, Zennosuke; Hirose, Hiromitsu

doi:10.1246/bcsj.41.2815

Cited by 493 publications

(246 citation statements)

References 2 publications

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“…3 In 1972, Anthony Baylis and Melville Hillman patented catalyzed reactions using similar tertiary amine. 4 In 1983, the reaction was rediscovered, and its scope was explored primarily by Drewes and Basavaiah.…”

Section: 2mentioning

confidence: 99%

The Baylis-Hillman reaction of substituted aminomethylbenzotriazoles

Katritzky¹,

Kim²,

Widyan³

2007

Arkivoc

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Section: 2mentioning

confidence: 99%

The Baylis-Hillman reaction of substituted aminomethylbenzotriazoles

Katritzky¹,

Kim²,

Widyan³

2007

Arkivoc

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“…[1][2][3][4][5] It involves the condensation of a carbon electrophile with the α position of an activated unsaturated compound (Scheme 1). Aldehydes, ketones and suitably protected imines (aza-MBH reaction) 6 are typical electrophilic components, while alkenes, alkynes and allenes substituted with a carbonyl-, carboxyl-, phosphonate-, or sulfonate-type functionality result in a diversity of unsaturated compounds.…”

Section: Introductionmentioning

confidence: 99%

P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

Talma¹,

Mucha²

2016

Arkivoc

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Morita-Baylis-Hillman adducts (e.g., activated allyl acetates or bromides) are an unprecedented trifunctional synthetic platform for diverse types of nucleophilic displacements, additions and rearrangements. These reactions can proceed in an inter-or intramolecular manner, and with stereoselective induction. Accordingly, they contribute, as the key steps, to numerous synthetic pathways, including the total syntheses of natural products of various classes and to novel strategies leading to medicinally relevant compounds and commercialized drugs. The synthetic feasibility of the Morita-Baylis-Hillman adducts in organophosphorus chemistry has been explored to a relatively low extent. In this review, we summarize the current state of the art on the formation of the C-P bond by means of the title reactions. The scope of the processes, the stereochemistry of the products and their further synthetic relevance to obtain multifunctional compounds, including those that are biologically active, are summarized.

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“…In contrast to the related Morita-Baylis-Hillman (MBH) and aza-MBH reactions, [2][3][4][5] wherein the latent enolate reacts with another aldehyde or imine, the RC reaction lacks reactivity and selectivity; using two distinct α,β-unsaturated carbonyl compounds leads to a mixture of homo-and heterocouplings.…”

mentioning

confidence: 99%

Chiral Organocatalyzed Intermolecular Rauhut–Currier Reaction of Nitroalkenes with Ethyl Allenoate

Takizawa

Sako

Kishi

et al. 2017

CHEMICAL & PHARMACEUTICAL BULLETIN

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An enantioselective intermolecular Rauhut-Currier (RC) reaction of nitroalkenes with ethyl allenoate has been established with quinidine-derived β-isocupreidine. The present RC reaction afforded α-functionalized allenoates 3 in up to 94% yield with 59% enantiomeric excess (ee). Key words Rauhut-Currier reaction; chiral organocatalysis; nitroalkene; α-functionalized allenoateThe Rauhut-Currier (RC) reaction 1,2) is a Lewis base-catalyzed carbon-carbon bond-forming reaction between two different α,β-unsaturated carbonyl compounds, wherein one compound acts as a latent enolate, providing α-substituted enones. In contrast to the related Morita-Baylis-Hillman (MBH) and aza-MBH reactions, [2][3][4][5] wherein the latent enolate reacts with another aldehyde or imine, the RC reaction lacks reactivity and selectivity; using two distinct α,β-unsaturated carbonyl compounds leads to a mixture of homo-and heterocouplings.Nitroalkenes are widely used as electron-deficient alkenes; they are employed in diverse organic reactions and act as Michael acceptors, dienophiles, and 1,3-dipoles.6) Despite the fact that nitroalkenes are excellent Michael acceptors, nitroalkenes mostly work as nucleophiles in the RC reaction because the Lewis base catalyst initially reacts at the β-position of the nitroalkene, resulting in the corresponding α-nucleophilic carbanion.7) In 2007, Henry and Kwon presented an achiral phosphine-catalyzed intramolecular RC reaction of a nitroalkene (Michael acceptor) and an allenoate (nucleophile) as a solitary example; in their system, sequential bond-formation took place after the intramolecular RC reaction, leading to a formation of the tricyclic product 8) (Chart 1a). Controlling chemoselectivity and imparting asymmetric induction to the product in the RC reaction of nitroalkenes and allenoates remain a challenging task.Herein we report the first chemo-, regio-, and enantioselective intermolecular RC reaction of allenoates 2 with nitroalkenes 1. Quinidine-derived β-isocupreidine (β-ICD) 9) was the optimal tested catalyst for the RC reaction, affording α-functionalized allenoates 3 10) with excellent yields under mild reaction conditions in a single operation (Chart 1b).As part of our efforts to explore enantioselective bifunctional catalysis, 11) we were interested in facile accesses to chiral α-substituted allenoates, which are useful platforms for the rapid asymmetric construction of complex molecules. 14) and β-ICD afforded the desired RC product 3a in moderate-to-good yields (entries 4 and 5). The RC reaction rate ordinarily increases in Brϕnsted acid.2) Although 2-naphthol (20 mol %) was added to the reaction mixture, the reaction rate decreased and the racemic form of 3a was obtained in less than 10% yield (entry 6). We also examined the catalytic effects of other cinchona alkaloid derivatives, however, no reaction was observed in any of the cases (entries 7 and 8).Encouraged by these results, we went on to study the effects of solvent on the reaction of 1a with 2a (Table 2). Ethereal solvents such a...

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A Tertiary Phosphine-catalyzed Reaction of Acrylic Compounds with Aldehydes

Cited by 493 publications

References 2 publications

The Baylis-Hillman reaction of substituted aminomethylbenzotriazoles

The Baylis-Hillman reaction of substituted aminomethylbenzotriazoles

P-C bond formation in reactions of Morita-Baylis-Hillman adducts with phosphorus nucleophiles

Chiral Organocatalyzed Intermolecular Rauhut–Currier Reaction of Nitroalkenes with Ethyl Allenoate

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