Tandem Remote Csp3–H Activation/Csp3–Csp3 Cleavage in Unstrained Aliphatic Chains Assisted by Palladium(II)

Pérez‐Gómez, Marta; Azizollahi, Hamid; Franzoni, Ivan; Larin, Egor M.; Lautens, Mark; Garcı́a-López, José-Antonio

doi:10.1021/acs.organomet.8b00920

Cited by 23 publications

(17 citation statements)

References 84 publications

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“…Lautens and Garcia‐Lopez have developed an interesting AQ‐directed strategy for the formation of alkenes 156 that involves remote C−H activation, carbene insertion and a key β‐carbon elimination step that furnishes the desired products along with a palladacycle still bearing the AQ directing group (Scheme 21 C). [107] …”

Section: Nucleophilic Cleavage Of the Amide Bondmentioning

confidence: 99%

A Guide to Directing Group Removal: 8‐Aminoquinoline

Fitzgerald

O’Duill

2021

Chemistry A European J

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The use of directing groups allows high levels of selectivity to be achieved in transition metal‐catalyzed transformations. Efficient removal of these auxiliaries after successful functionalization, however, can be very challenging. This review provides a critical overview of strategies used for removal of Daugulis’ 8‐aminoquinoline (2005–2020), one of the most widely used N,N‐bidentate directing groups. The limitations of these strategies are discussed and alternative approaches are suggested for challenging substrates. Our aim is to provide a comprehensive end‐users’ guide for chemists in academia and industry who want to harness the synthetic power of directing groups—and be able to remove them from their final products.

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Section: Nucleophilic Cleavage Of the Amide Bondmentioning

confidence: 99%

A Guide to Directing Group Removal: 8‐Aminoquinoline

Fitzgerald

O’Duill

2021

Chemistry A European J

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“…Related to Engle’s work, a stoichiometric study on the Pd-mediated Csp 3 –H activation/Csp 3 –Csp 3 bond cleavage on 8-aminoquinolyl amide substrates 393 was reported by Lautens, García-López and co-workers ( Scheme 52 ) [ 137 ]. C , N , N -pincer palladacycles 397 , obtained upon Csp 3 –H activation of substrates 393 by reaction with Pd(OAc) 2 , reacted with carbene precursors such as diazocarbonyl compounds 394 .…”

Section: Synthetic Methodology Involving C–h Functionalization Alomentioning

confidence: 99%

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Azizollahi

Garcı́a-López

2020

Molecules

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The functionalization of C–H bonds has become a major thread of research in organic synthesis that can be assessed from different angles, for instance depending on the type of catalyst employed or the overall transformation that is carried out. This review compiles recent progress in synthetic methodology that merges the functionalization of C–H bonds along with the cleavage of C–C bonds, either in intra- or intermolecular fashion. The manuscript is organized in two main sections according to the type of substrate in which the cleavage of the C–C bond takes place, basically attending to the scission of strained or unstrained C–C bonds. Furthermore, the related research works have been grouped on the basis of the mechanistic aspects of the different transformations that are carried out, i.e.,: (a) classic transition metal catalysis where organometallic intermediates are involved; (b) processes occurring via radical intermediates generated through the use of radical initiators or photochemically; and (c) reactions that are catalyzed or mediated by suitable Lewis or Brønsted acid or bases, where molecular rearrangements take place. Thus, throughout the review a wide range of synthetic approaches show that the combination of C–H and C–C cleavage in single synthetic operations can serve as a platform to achieve complex molecular skeletons in a straightforward manner, among them interesting carbo- and heterocyclic scaffolds.

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“…In 2019, García-López, Lautens, and coworkers reported a directed and palladium-mediated activation of unstrained C(alkyl)-C(alkyl) bonds in linear amides. 97 While this is not a catalytic reaction and uses stoichiometric palladium, it is nevertheless included here as an exception due to its novel reaction mode. This reaction employed 8-aminoquinoline-derived aliphatic amides (85) as the substrate, which reacted with 1 equiv.…”

Section: Dgs Removed In the Catalytic Cyclementioning

confidence: 99%

Temporary or removable directing groups enable activation of unstrained C–C bonds

2020

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Carbon−carbon (C-C) bonds constitute basic skeletons in most organic molecules. One can imagine that selective manipulation of C-C bonds would provide a direct approach to edit or alter molecular scaffolds but has been an ongoing challenge. Due to the kinetic inertness of C-C bonds, the common strategies of activating these bonds by transition metals rely on either the use of highly strained substrates or the assistance of a permanent directing group (DG), in which strain relief or formation of stable metallocycles becomes the driving force. To allow more common and less strained compounds utilized as substrates for C-C activation, the use of temporary and removable DGs has emerged as an attractive strategy in the past two decades. A variety of C−C bonds in unstrained or less strained organic molecules now can be converted to more reactive metal-carbon bonds, and further downstream transformations have led to diverse synthetic methods. This review highlights the development of catalytic approaches that can activate unstrained C-C bonds enabled by temporary or removable DGs. The content is mainly divided based on the nature of the DGs: temporary and removable. Applications of these methods in syntheses of natural products or bioactive molecules are also discussed.

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Tandem Remote Csp³–H Activation/Csp³–Csp³ Cleavage in Unstrained Aliphatic Chains Assisted by Palladium(II)

Cited by 23 publications

References 84 publications

A Guide to Directing Group Removal: 8‐Aminoquinoline

A Guide to Directing Group Removal: 8‐Aminoquinoline

Recent Advances on Synthetic Methodology Merging C–H Functionalization and C–C Cleavage

Temporary or removable directing groups enable activation of unstrained C–C bonds

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