Vinylidenation of Organoboronic Esters Enabled by a Pd‐Catalyzed Metallate Shift

Aparece, Mark D.; Gao, Chenpeng; Lovinger, Gabriel J.; Morken, James P.

doi:10.1002/ange.201811782

Cited by 13 publications

(4 citation statements)

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“…67 These include boron groups, which are highly relevant for coupling reactions. 68–70 Additionally, the catalyst is not poisoned by sulfur atoms in the substrate, which is a common problem in heterogeneous hydrogenation catalysis. 71,72…”

Section: Resultsmentioning

confidence: 99%

“…67 These include boron groups, which are highly relevant for coupling reactions. [68][69][70] Additionally, the catalyst is not poisoned by sulfur atoms in the substrate, which is a common problem in heterogeneous hydrogenation catalysis. 71,72 A very interesting selectivity feature was observed during the substrate screening: if the molecule offered more than one nitro group, only one nitro moiety was reduced in all cases.…”

Section: View Article Onlinementioning

confidence: 99%

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Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste

Unglaube

Schlapp

Quade

et al. 2022

Catal. Sci. Technol.

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Section: Resultsmentioning

confidence: 99%

Section: View Article Onlinementioning

confidence: 99%

Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste

Unglaube

Schlapp

Quade

et al. 2022

Catal. Sci. Technol.

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“…30 Alternatively, β-hydrogen elimination of the organometallic intermediate would afford an alkenylboronic ester. 31…”

Section: Other Reactions Involving the Zweifel Olefination Mechanismmentioning

confidence: 99%

Recent Progress on the Zweifel Olefination: An Update

Song,

2023

Synthesis

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During the past several decades, Zweifel olefination has emerged as one of the most powerful and reliable tools for constructing C–C double bonds. This reaction features high efficiency, good versatility, nonuse of transition metals, and perfect stereospecificity, which make it superior to many other olefination methods. Since the summary of Zweifel olefination’s 50-years history was published in 2017 by Aggarwal et al., remarkable achievements have been made in terms of employing new organometallic species, proceeding through electrochemical or photochemical pathways, and furnishing new kinds of products. This short review summarizes and discusses the very recent progress in Zweifel olefination and its latest application in natural products synthesis. 1 Introduction 2 Zweifel Olefination with New Organometallic Species 3 Zweifel Olefination with New Migrating Groups 4 Electrochemical and Photocatalyzed Zweifel Olefination 5 New Elimination and Migration Patterns of Zweifel Olefination 6 Zweifel Olefination in Natural Product Synthesis 7 Other Reactions Involving the Zweifel Olefination Mechanism 8 Conclusions and Outlook

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“…10 Likewise, alkenyl boronic esters and their derivatives typically display good air and moisture stability that allow for ease of preparation and isolation. 11,12,13,14,15 Alkenyl boronate complexes can participate in threecomponent couplings through two related mechanistic manifolds. They can engage with electrophiles in a concerted mechanism, wherein an external electrophilic activator promotes migration of the organic fragment onto the adjacent sp 2 -hybridized carbon (Scheme 1a) .…”

Section: Introductionmentioning

confidence: 99%

Mechanistic basis for the Iridium-Catalyzed Enantioselective Al-lylation of Alkenyl Boronates

Davis

Ready

2022

Preprint

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Iridium(phosphoramidite) complexes catalyze an enantio- and diastereoselective three-component coupling reaction of alkenyl boronic esters, organolithium reagents and secondary allylic aryl carbonates. The reaction proceeds through an allylation-induced 1,2-metalate shift of the alkenyl boronate forming non-adjacent stereocenters. Mechanistic investiga-tions outline the overall catalytic cycle and reveal trends in reactivity and selectivity. Analysis of relative stereochemistry in a variety of 1,1-disubtituted alkenyl boronates provides insight into the transition state of the addition and indicates a concerted pathway. Kinetic analysis of the reaction revealed the kinetic order dependance in boronate, catalyst, and both the slow- and fast-reacting enantiomer of allylic carbonate as well as the turnover-limiting step of the reaction. Hammett studies explored substituent effects in both aryl-derived alkenyl boronates and aryl carbonates. Initial investigations into the migratory selectivity of the 1,2-metalate shift were also examined using (bis)alkenyl boronates.

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Vinylidenation of Organoboronic Esters Enabled by a Pd‐Catalyzed Metallate Shift

Cited by 13 publications

References 53 publications

Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste

Highly active heterogeneous hydrogenation catalysts prepared from cobalt complexes and rice husk waste

Recent Progress on the Zweifel Olefination: An Update

Mechanistic basis for the Iridium-Catalyzed Enantioselective Al-lylation of Alkenyl Boronates

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