Phosphoramidites Are Efficient, Green Organocatalysts for the Michael Reaction. Mechanistic Insights into the Phosphorus‐Catalyzed Michael Reaction of Alkynones and Implications for Asymmetric Catalysis.

Grossman, Robert B.; Comesse, Sébastien; Rasne, Ravindra M.; Hattori, Katsumi; Delong, Matthew N.

doi:10.1002/chin.200324063

Cited by 2 publications

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References 2 publications

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“…Ten years after Inanaga's report, Grossman demonstrated the efficient Michael additions of carbon pronucleophiles under phosphine catalysis. 468 HMPA, a strongly nucleophilic phosphine, was the choice of the promoter for these reactions (Scheme 401). When 3-butyn-2-one was employed as the electrophile, high yields were obtained of the Michael adducts, favoring the Z-isomers (entry 1).…”

Section: Phosphine-catalyzed Isomerization Of Alkynes To Dienesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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The hallmark of nucleophilic phosphine catalysis is the initial nucleophilic addition of a phosphine to an electrophilic starting material, producing a reactive zwitterionic intermediate, generally under mild conditions. In this Review, we classify nucleophilic phosphine catalysis reactions in terms of their electrophilic components. In the majority of cases, these electrophiles possess carbon–carbon multiple bonds: alkenes (section 2), allenes (section 3), alkynes (section 4), and Morita–Baylis–Hillman (MBH) alcohol derivatives (MBHADs; section 5). Within each of these sections, the reactions are compiled based on the nature of the second starting material—nucleophiles, dinucleophiles, electrophiles, and electrophile–nucleophiles. Nucleophilic phosphine catalysis reactions that occur via the initial addition to starting materials that do not possess carbon–carbon multiple bonds are collated in section 6. Although not catalytic in the phosphine, the formation of ylides through the nucleophilic addition of phosphines to carbon–carbon multiple bond–containing compounds is intimately related to the catalysis and is discussed in section 7. Finally, section 8 compiles miscellaneous topics, including annulations of the Hüisgen zwitterion, phosphine-mediated reductions, iminophosphorane organocatalysis, and catalytic variants of classical phosphine oxide–generating reactions.

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Section: Phosphine-catalyzed Isomerization Of Alkynes To Dienesmentioning

confidence: 99%

Phosphine Organocatalysis

et al. 2018

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“…4 Impressively, a slight variation of the structure of substrates often deviates generic reaction patterns, resulting in unforeseen reactivity. For instance, whereas propionates mainly undergo phosphine-catalyzed α-addition 5 and β-addition 6 reactions via an intermediate A (Scheme 1a), butynoates or allenoates are prone to γ-addition 7 and [3 + n] annulations 4a,8 through a zwitterion B (Scheme 1b). Notably, the installation of a δ-carbon on the allenoates brings about a new species C, resulting in [3 + 2] 9 and [4 + 2] 10 annulations and isomerization 11 with δ-carbon participating in the reaction (Scheme 1c).…”

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Phosphine-Catalyzed Internal Redox [4 + 2] Annulation between 1,4-Enynoates and Electron-Deficient Alkenes

Cheng

Tang

et al. 2021

Org. Lett.

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Herein we describe a phosphine-catalyzed internal redox [4 + 2] annulation of 1,4-enynoates with electron-deficient alkenes, in which the γand φ-C(sp 3 )−H of the enynoates are formally oxidized for the annulation while the alkynyl moiety is converted to an alkene. The reaction offers an efficient synthesis of highly functionalized cyclohexenes in moderate to good yields with exclusive regioselectivity and high diastereoselectivity under mild conditions.

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Phosphoramidites Are Efficient, Green Organocatalysts for the Michael Reaction. Mechanistic Insights into the Phosphorus‐Catalyzed Michael Reaction of Alkynones and Implications for Asymmetric Catalysis.

Cited by 2 publications

References 2 publications

Phosphine Organocatalysis

Phosphine Organocatalysis

Phosphine-Catalyzed Internal Redox [4 + 2] Annulation between 1,4-Enynoates and Electron-Deficient Alkenes

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