Recent Developments in Intermolecular Cross‐Rauhut‐Currier Reactions

Biswas, Subhankar; Bania, Nimisha; Pan, Subhas Chandra

doi:10.1002/tcr.202200257

Cited by 7 publications

(2 citation statements)

References 45 publications

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“…They are widely used as ligands, catalysts, or reagents in a myriad of chemical reactions . Particularly, various transformations based on the nucleophilicity of organophosphines have been developed, as exemplified by a number of name reactions including Staudinger, Wittig, Mitsunobu, Rauhut–Currier, Appel, Michaelis–Arbuzov, and Lu’s [3 + 2] reactions. While organophosphine-mediated reactions have found widespread applications in both academia and industry, some of them, such as the Wittig reaction, suffer from an inherent drawback: stoichiometric organophosphine reagents have to be employed, as they will transform into nonproductive phosphine oxides at the end of reactions.…”

Section: Introductionmentioning

confidence: 99%

Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction

Zhang,

Kong,

Guo

et al. 2024

J. Am. Chem. Soc.

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The reaction mechanism of Brønsted acid-catalyzed silane-dependent PO reduction has been elucidated through combined computational and experimental methods. Due to its remarkable chemo- and stereoselective nature, the Brønsted acid/silane reduction system has been widely employed in organophosphine-catalyzed transformations involving P(V)/P(III) redox cycle. However, the full mechanistic profile of this type of PO reduction has yet to be clearly established to date. Supported by both DFT and experimental studies, our research reveals that the reaction likely proceeds through mechanisms other than the widely accepted “dual activation mode by silyl ester” or “acid-mediated direct PO activation” mechanism. We propose that although the reduction mechanisms may vary with the substitution patterns of silane species, Brønsted acid generally activates the silane rather than the PO group in transition structures. The proposed activation mode differs significantly from that associated with traditional Brønsted acid-catalyzed CO reduction. The uniqueness of PO reduction originates from the dominant Si/OP orbital interactions in transition structures rather than the P/H–Si interactions. The comprehensive mechanistic landscape provided by us will serve as a guidance for the rational design and development of more efficient PO reduction systems as well as novel organophosphine-catalyzed reactions involving P(V)/P(III) redox cycle.

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Section: Introductionmentioning

confidence: 99%

Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction

Zhang,

Kong,

Guo

et al. 2024

J. Am. Chem. Soc.

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“…3 In light of these considerations, the Rauhut−Currier (RC) reaction, also known as the Morita−Baylis−Hillman vinylogous reaction, has emerged as a powerful synthetic method for increasing molecular diversity. 4 Mechanistically, this reaction involves the conjugate addition of an enolate, generated in situ from the addition of a nucleophilic catalyst on a first Michael acceptor (RC donor) to a second Michael acceptor (RC acceptor). Subsequent proton transfer and regeneration of the active catalyst through a retro-Michael reaction leads to the targeted unsaturated cyclic compounds (Scheme 1).…”

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confidence: 99%

Carbon Nucleophile-Initiated Rauhut–Currier Reaction: An Atom-Economical Synthesis of Highly Functionalized Carbocycles

2023

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Phosphine-Catalyzed Crossed Rauhut–Currier-Type Coupling and [3 + 2]-Cycloaddition of 2-Alkylidene-3-oxindoles with Alkenes and Allenes to Access β,γ-Unsaturated Enones and Polycyclic Oxindoles

Banda,

Johannßen,

Voss

et al. 2024

J. Org. Chem.

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Dihydroazepino[1,indole diones are tricyclic Nacyl-2-alkylidene-3-oxindole enones that readily engage in tertiary phosphine-catalyzed intermolecular coupling reactions with acceptor-substituted alkenes. In these reactions, the tricyclic αsubstituted enones undergo an α-alkylation with concomitant formation of a quaternary stereocenter, as well as the installation of a new double bond within the seven-membered azepane ring. The organocatalytic reaction constitutes a special case of the crossed intermolecular Rauhut−Currier reaction as the presence of the α-substituent in the enones prohibits the formation of an α,βunsaturated product, but instead, skipped β,γ-unsaturated enones are obtained. With allene carboxylates as alternative coupling partners, the crossed Rauhut−Currier-type reaction competes with a regioselective allene to enone [3 + 2]-cycloaddition, and the product selectivity can be controlled by the choice of the phosphine organocatalyst.

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Recent Developments in Intermolecular Cross‐Rauhut‐Currier Reactions

Cited by 7 publications

References 45 publications

Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction

Combined Computational and Experimental Study Reveals Complex Mechanistic Landscape of Brønsted Acid-Catalyzed Silane-Dependent P═O Reduction

Carbon Nucleophile-Initiated Rauhut–Currier Reaction: An Atom-Economical Synthesis of Highly Functionalized Carbocycles

Phosphine-Catalyzed Crossed Rauhut–Currier-Type Coupling and [3 + 2]-Cycloaddition of 2-Alkylidene-3-oxindoles with Alkenes and Allenes to Access β,γ-Unsaturated Enones and Polycyclic Oxindoles

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