A Family of Chiral Ferrocenyl Diols: Modular Synthesis, Solid‐State Characterization, and Application in Asymmetric Organocatalysis

Nottingham, Chris; Müller‐Bunz, Helge; Guiry, Patrick J.

doi:10.1002/ange.201604840

Cited by 9 publications

(5 citation statements)

References 41 publications

(6 reference statements)

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“…Recently, Guiry and co-workers applied this methodology to the synthesis of a new family of chiral ferrocenyl diols from dibromide 13 (Scheme 8). 43 Both the prior reports from the groups of Gu and You 40 and Kang and Gu, 41 had disclosed the synthesis of the C 2 symmetric dione 14 in excellent enantioselectivity via a double cyclization event. Further optimization by Guiry et al enabled a multigram, chromatography-free synthesis of this key intermediate, while simultaneously decreasing catalyst and ligand loadings.…”

Section: Stereochemistry-generating C−h Activationmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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The development of new methods for the direct functionalization of unactivated C-H bonds is ushering in a paradigm shift in the field of retrosynthetic analysis. In particular, the catalytic enantioselective functionalization of C-H bonds represents a highly atom- and step-economic approach toward the generation of structural complexity. However, as a result of their ubiquity and low reactivity, controlling both the chemo- and stereoselectivity of such processes constitutes a significant challenge. Herein we comprehensively review all asymmetric transition-metal-catalyzed methodologies that are believed to proceed via an inner-sphere-type mechanism, with an emphasis on the nature of stereochemistry generation. Our analysis serves to document the considerable and rapid progress within in the field, while also highlighting limitations of current methods.

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Section: Stereochemistry-generating C−h Activationmentioning

confidence: 99%

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

et al. 2017

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“…The resulting ferrocene derivatives were obtained in up to 99% yield and 99% ee under mild conditions. Interestingly, by applying this method, Guiry and coworkers prepared a new family of planar chiral ferrocenyl diols, which have been shown to be effective catalysts for asymmetric hetero-Diels-Alder reactions [74]. Around the same time, Gu, Kang, and coworkers disclosed the efficient synthesis of planar chiral ferrocenes from aryl iodides under similar conditions.…”

Section: Pd(0)-catalyzed Asymmetric C-h Bond Functionalization Of Ferrocenesmentioning

confidence: 99%

Asymmetric C–H Bond Functionalization of Ferrocenes: New Opportunities and Challenges

Liu

You

2020

Trends in Chemistry

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“…Interestingly, starting from 19a, Guiry and co-workers prepared a novel family of planar-chiral ferrocenyl diols, which were demonstrated to serve as efficient catalysts in asymmetric hetero-Diels−Alder reactions that generate cycloadducts in moderate yields with up to 92% ee (Scheme 11B). 25 About the same time, Gu, Kang, and co-workers reported using a similar strategy to design a process for the efficient synthesis of planar chiral ferrocenes from aryl iodides. 26 Besides ferrocenes, ruthenocene derivatives also serve as suitable substrates.…”

Section: Enantioselective Synthesis Of Planar Chiral Ferrocenes Via P...mentioning

confidence: 99%

Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C–H Bond Functionalization

et al. 2017

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Ferrocenes are of great interest in the fields of materials science, organic synthesis, and biomedical research. Of particular significance is the fact that ferrocenes bearing planar chirality have been demonstrated to be highly efficient ligands or catalysts in asymmetric catalysis, some of which have been employed in the industrial synthesis of pharmaceuticals and agrochemicals. So far, the main methods for the synthesis of planar chiral ferrocenes involve diastereoselective directed ortho-metalation (DoM), enantioselective DoM, and chiral resolution. Despite the fact that these approaches are well developed and widely applied, the use of chiral auxiliaries or external stoichiometric chiral bases is required in most cases. Additionally, the practicality of these processes is hampered by the requirement of sensitive organometallic reagents, the poor compatibility with functional groups, and the low atom economy in some cases. Therefore, the development of highly efficient strategies to introduce planar chirality on the backbone of ferrocene that do not possess these limitations is highly desirable. Meanwhile, transition-metal-catalyzed asymmetric C-H bond functionalization reactions have attracted much attention over the past few years owing to their emerging potential for providing a straightforward approach for the preparation of chiral molecules. In addition to the majority of the work focusing on the installation of central chirality, methods for the catalytic asymmetric synthesis of planar chiral compounds via C-H bond functionalization have also been explored. In this Account, we summarize our recent efforts aimed at the development of novel methods to synthesize planar chiral compounds via asymmetric C-H bond functionalization and also highlight related achievements by other groups. First, we briefly introduce the precedent examples of diastereoselective and enantioselective synthesis of planar chiral ferrocenes. Subsequently, asymmetric syntheses of structurally diverse planar chiral ferrocenes via Pd [Pd(II), Pd(0)]-, Ir-, Rh-, Au-, and Pt-catalyzed C-H bond functionalization are described. These methods have impressive advantages over traditional approaches for the synthesis of functionalized planar chiral ferrocenes in terms of both step- and atom-economies. Notably, the products of these processes are easily transformed into a variety of new catalysts or ligands, which have been demonstrated to promote efficient asymmetric reactions. Moreover, DFT calculations have been conducted to explore the origin of the excellent enantioselectivity of Pd-catalyzed enantioselective C-H bond functionalization reactions. Progress made in the area of asymmetric C-H bond functionalization provides an effective platform for the design and synthesis of planar chiral ferrocenes.

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A Family of Chiral Ferrocenyl Diols: Modular Synthesis, Solid‐State Characterization, and Application in Asymmetric Organocatalysis

Cited by 9 publications

References 41 publications

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Catalytic Enantioselective Transformations Involving C–H Bond Cleavage by Transition-Metal Complexes

Asymmetric C–H Bond Functionalization of Ferrocenes: New Opportunities and Challenges

Synthesis of Planar Chiral Ferrocenes via Transition-Metal-Catalyzed Direct C–H Bond Functionalization

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