Rhodium(I)‐Catalyzed Intermolecular Hydroacylation of α‐Keto Amides and Isatins with Non‐Chelating Aldehydes

Kou, Kevin G. M.; Longobardi, Lauren E.; Dong, Vy M.

doi:10.1002/adsc.201500313

Cited by 16 publications

(13 citation statements)

References 64 publications

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“…Achiral Rh(I) catalysts were later applied to the synthesis of racemic products to expand upon the types of α -ketoamides, isatins and α -branched aldehydes that could be employed. 77 …”

Section: Ketonesmentioning

confidence: 99%

“…Upon investigating aldehyde scope, the authors established that a number of alkyl derivatives were competent C–H bond activation substrates, with linear, α- and β-branched derivatives all providing good to excellent yields and enantioselectivities. Achiral Rh(I) catalysts were later applied to the synthesis of racemic products to expand upon the types of α-ketoamides, isatins, and α-branched aldehydes that could be employed …”

Section: Ketonesmentioning

confidence: 99%

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Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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The transition metal-catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds has emerged as a particularly efficient and powerful approach for the construction of an incredibly diverse array of heteroatom substituted products. Readily available and stable inputs are typically employed, and reactions often proceed with very high functionality group compatibility and without the production of waste byproducts. Additionally, many transition metal-catalyzed C–H bond additions to polarized π-bonds occur within cascade reaction sequences to provide rapid access to a diverse array of different heterocyclic as well as carbocyclic products. This review highlights the diversity of transformations that have been achieved, catalysts that have been used, and types of products that have been prepared through the transition metal catalyzed addition of C–H bonds to carbonyls, imines and related polarized π-bonds.

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“…Achiral Rh(I) catalysts were later applied to the synthesis of racemic products to expand upon the types of α -ketoamides, isatins and α -branched aldehydes that could be employed. 77 …”

Section: Ketonesmentioning

confidence: 99%

Section: Ketonesmentioning

confidence: 99%

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

2016

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“…The transition-metal-catalyzed hydroacylation of miscellaneous unsaturated hydrocarbons and carbonyl compounds involving aldehyde C–H bond activation has been recognized as one of the most robust and valuable organic transformations for direct C–C and C–O bond formation, and the products afforded therefrom have had an extraordinarily impressive impact on the research and development of original branded pharmaceuticals. In comparison with the substantially investigated hydroacylation reactions of alkenes, alkynes, and other conjugated unsaturated hydrocarbons for ketone synthesis, the complementary hydroacylation ultimately leading to ester products remains a less advanced reaction class, although several catalytic systems have been demonstrated that employ ketones as the starting materials . Consequently, the development of ketones and their counterparts for highly efficient and completely atom-economical hydroacylation would be both desirable and challenging.…”

mentioning

confidence: 99%

“… Over the last few decades, transparent efforts have been exerted on the highly efficient synthesis of these value-added esters by virtue of metal-catalyzed cross-coupling tactics (Scheme ). Classical intra- and intermolecular carbonyl hydroacylation in the presence of rhodium(I), , nickel(0), ruthenium(II), and samarium(II) catalysis is one of the most comprehensively used approaches, and it constitutes a significant technology in the straightforward and atom-economical preparation of esters (Scheme a), albeit with inherent challenges yet to be overcome, such as the decarbonylation and aldol reactions. Alternatively, by taking advantage of the ruthenium(0) and palladium(II) catalytic systems, the hydroesterification reactions of alkenes with formates can occur to afford the desired products through the activation of the formyl C–H bond (Scheme b).…”

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confidence: 99%

Rhodium-Catalyzed Regioselective Formal Hydroacylation of Vinyl Epoxides toward Esters Involving β-Carbon Cleavage

et al. 2021

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Herein we disclose the first example of the formal hydroacylation reactions of vinyl epoxides with chelating aldehydes enabled by rhodium catalysis for the efficient construction of functionalized esters. Detailed investigations of the mechanistic pathway reveal that the presence of a 2-vinyl group is essential in contributing to the success of this regioselective reaction, which might proceed through β-carbon cleavage as the key procedure.

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“…In a follow-up study, we prepared a novel dcpp-inspired bisphosphine ligand (L5) that contains two Pstereogenic centers. 50 This bidentate ligand for Rh expands the scope to include isatins and linear α-ketoamides with aliphatic aldehydes.…”

Section: Intermolecular Carbonyl Hydroacylationmentioning

confidence: 99%

Teaching Aldehydes New Tricks Using Rhodium- and Cobalt-Hydride Catalysis

2021

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Conspectus By using transition metal catalysts, chemists have altered the “logic of chemical synthesis” by enabling the functionalization of carbon–hydrogen bonds, which have traditionally been considered inert. Within this framework, our laboratory has been fascinated by the potential for aldehyde C–H bond activation. Our approach focused on generating acyl-metal-hydrides by oxidative addition of the formyl C–H bond, which is an elementary step first validated by Tsuji in 1965. In this Account, we review our efforts to overcome limitations in hydroacylation. Initial studies resulted in new variants of hydroacylation and ultimately spurred the development of related transformations (e.g., carboacylation, cycloisomerization, and transfer hydroformylation). Sakai and co-workers demonstrated the first hydroacylation of olefins when they reported that 4-pentenals cyclized to cyclopentanones, using stoichiometric amounts of Wilkinson’s catalyst. This discovery sparked significant interest in hydroacylation, especially for the enantioselective and catalytic construction of cyclopentanones. Our research focused on expanding the asymmetric variants to access medium-sized rings (e.g., seven- and eight-membered rings). In addition, we achieved selective intermolecular couplings by incorporating directing groups onto the olefin partner. Along the way, we identified Rh and Co catalysts that transform dienyl aldehydes into a variety of unique carbocycles, such as cyclopentanones, bicyclic ketones, cyclohexenyl aldehydes, and cyclobutanones. Building on the insights gained from olefin hydroacylation, we demonstrated the first highly enantioselective hydroacylation of carbonyls. For example, we demonstrated that ketoaldehydes can cyclize to form lactones with high regio- and enantioselectivity. Following these reports, we reported the first intermolecular example that occurs with high stereocontrol. Ketoamides undergo intermolecular carbonyl hydroacylation to furnish α-acyloxyamides that contain a depsipeptide linkage. Finally, we describe how the key acyl-metal-hydride species can be diverted to achieve a C–C bond-cleaving process. Transfer hydroformylation enables the preparation of olefins from aldehydes by a dehomologation mechanism. Release of ring strain in the olefin acceptor offers a driving force for the isodesmic transfer of CO and H2. Mechanistic studies suggest that the counterion serves as a proton-shuttle to enable transfer hydroformylation. Collectively, our studies showcase how transition metal catalysis can transform a common functional group, in this case aldehydes, into structurally distinct motifs. Fine-tuning the coordination sphere of an acyl-metal-hydride species can promote C–C and C–O bond-forming reactions, as well as C–C bond-cleaving processes.

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Rhodium(I)‐Catalyzed Intermolecular Hydroacylation of α‐Keto Amides and Isatins with Non‐Chelating Aldehydes

Cited by 16 publications

References 64 publications

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Transition-Metal-Catalyzed C–H Bond Addition to Carbonyls, Imines, and Related Polarized π Bonds

Rhodium-Catalyzed Regioselective Formal Hydroacylation of Vinyl Epoxides toward Esters Involving β-Carbon Cleavage

Teaching Aldehydes New Tricks Using Rhodium- and Cobalt-Hydride Catalysis

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