Rhodium(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C–H Activation

Phipps, Erik J. T.; Piou, Tiffany; Rovis, Tomislav

doi:10.1055/s-0039-1690130

Cited by 15 publications

(5 citation statements)

References 27 publications

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“…The diastereoselectivity of this transformation probably arises from an intermediate generated from the ring-opening acylation of allylic alcohol. Meanwhile, Rovis and co-worker also achieved a similar cyclopropanation protocol for N -enoxyphthalimides and unbiased olefins under modified conditions …”

Section: Alkenyl C–h Bond Functionalization Of Alkenes Containing a H...mentioning

confidence: 99%

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

et al. 2022

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Alkenes and their derivatives are featured widely in a variety of natural products, pharmaceuticals, and advanced materials. Significant efforts have been made toward the development of new and practical methods to access this important class of compounds by selectively activating the alkenyl C(sp2)–H bonds in recent years. In this comprehensive review, we describe the state-of-the-art strategies for the direct functionalization of alkenyl sp2 C–H and C–F bonds until June 2022. Moreover, metal-free, photoredox, and electrochemical strategies are also covered. For clarity, this review has been divided into two parts; the first part focuses on currently available alkenyl sp2 C–H functionalization methods using different alkene derivatives as the starting materials, and the second part describes the alkenyl sp2 C–F bond functionalization using easily accessible gem-difluoroalkenes as the starting material. This review includes the scope, limitations, mechanistic studies, stereoselective control (using directing groups as well as metal-migration strategies), and their applications to complex molecule synthesis where appropriate. Overall, this comprehensive review aims to document the considerable advancements, current status, and emerging work by critically summarizing the contributions of researchers working in this fascinating area and is expected to stimulate novel, innovative, and broadly applicable strategies for alkenyl sp2 C–H and C–F bond functionalizations in the coming years.

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Section: Alkenyl C–h Bond Functionalization Of Alkenes Containing a H...mentioning

confidence: 99%

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

et al. 2022

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“…Liu and Chen [46] have elucidated both carboamination and cyclopropanation mechanisms in a DFT study of the Cp tBu Rh III catalyst. Since that time, other proposals have been put forward, including an alternative cyclopropanation proposed by Rovis [47] as well as an ionic mechanism where the hydroxamate moiety is deprotonated by an acetate ion prior to metal coordination [48] (for the carboamination pathway). After testing multiple possibilities for both the carboamination and cyclopropanation pathways, the lowest energy catalytic cycles were identified as those depicted in Scheme 2 (see Supporting Information, Figures S1 and S2 for the relative energies of these alternative pathways).…”

Section: Resultsmentioning

confidence: 99%

Mapping Catalyst–Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions

Wodrich

Chang

Gallarati

et al. 2022

Chemistry A European J

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Group 9 metals, in particular Rh III complexes with cyclopentadienyl ligands, are competent CÀ H activation catalysts. Recently, a Cp*Rh III -catalyzed reaction of alkenes with N-enoxyphthalimides showed divergent outcome based on the solvent, with carboamination favored in methanol and cyclopropanation in 2,2,2-trifluoroethanol (TFE). Here, we create selectivity and activity maps capable of unravelling the catalyst-solvent interplay on the outcome of these competing reactions by analyzing 42 cyclopentadienyl metal catalysts, Cp X M III (M = Co, Rh, Ir). These maps not only can be used to rationalize previously reported experimental results, but also capably predict the behavior of untested catalyst/solvent combinations as well as aid in identifying experimental protocols that simultaneously optimize both catalytic activity and selectivity (solutions in the Pareto front). In this regard, we demonstrate how and why the experimentally employed Cp*Rh III catalyst represents an ideal choice to invoke a solvent-induced change in reactivity. Additionally, the maps reveal the degree to which even perceived minor changes in the solvent (e. g., replacing methanol with ethanol) influence the ratio of carboamination and cyclopropanation products. Overall, the selectivity and activity maps presented here provide a generalizable tool to create global pictures of anticipated reaction outcome that can be used to develop new experimental protocols spanning metal, ligand, and solvent space.

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“…The known approaches to the synthesis of 1,5-substituted spiro [2.3]hexanes rely on the construction of either three-or four-membered ring, [19][20][21][22][23] the former strategy being more popular (Scheme 1). In particular, Zefirov, Yashin, Averina, and co-workers applied it to the synthesis of a series of amino acids, [24][25][26][27][28][29][30] including spirocyclic GABA analogues.…”

Section: Introductionmentioning

confidence: 99%

Monoprotected Diamines Derived from 1,5‐Disubstituted (Aza)spiro[2.3]hexane Scaffolds

et al. 2021

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Synthesis of monoprotected diamines derived from 1,5-disubstituted spiro[2.3]hexane and 5-azaspiro[2.3]hexane scaffolds is described. In both cases, the method relied on the cyclopropanation of the corresponding cyclobutane or azetidine derivatives. In the case of monoprotected 1,5-diaminospiro[2.3] hexanes, the title products were obtained as single diastereomers. X-Ray diffraction studies supported by exit vector plot (EVP) analysis showed that the obtained building blocks are promising piperidine/cycloalkane isosteres with potential utility to drug discovery. Also, conformations observed in the crystalline state for the two different diastereomers of 1,5-diaminospiro [2.3]hexane derivatives prompt their application in design of βturn and sheet-like peptidomimetics, respectively.

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Rhodium(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C–H Activation

Cited by 15 publications

References 27 publications

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Mapping Catalyst–Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions

Monoprotected Diamines Derived from 1,5‐Disubstituted (Aza)spiro[2.3]hexane Scaffolds

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Rhodium(III)-Catalyzed Cyclopropanation of Unactivated Olefins Initiated by C–H Activation

Cited by 15 publications

References 27 publications

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp2 C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Mapping Catalyst–Solvent Interplay in Competing Carboamination/Cyclopropanation Reactions

Monoprotected Diamines Derived from 1,5‐Disubstituted (Aza)spiro[2.3]hexane Scaffolds

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Product

Resources

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Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications

Recent Advances in Alkenyl sp² C–H and C–F Bond Functionalizations: Scope, Mechanism, and Applications