Mechanistic investigation into the C(sp<sup>3</sup>)–H acetoxylation of morpholinones

Buettner, Cornelia S.; Willcox, Darren; Chappell, Ben; Gaunt, Matthew J.

doi:10.1039/c8sc03434f

Cited by 27 publications

(19 citation statements)

References 32 publications

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“…On the basis of our observations and previous reports, a plausible mechanism for this reaction is outlined in Scheme . We believe that during the reaction initially complex 12 is formed by the cyclo‐palladation of 1 a with Pd(OAc) 2 with the elimination of acetic acid.…”

Section: Resultssupporting

confidence: 62%

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

Gupta

Kumar

et al. 2019

ChemistrySelect

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A highly efficient, palladium‐catalyzed protocol for the regioselective ortho‐acyloxylation of 4H‐Benzo[d][1,3]oxazin‐4‐ones and various other heterocycles which includes indoline, 3,4‐dihydro‐2H‐benzo[b][1,4]oxazine, and 1‐methyl‐3‐phenylquinoxalin‐2(1H)‐one has been developed using C−H activation strategy. The protocol exploits the directing group property of nitrogen present in the heterocyclic framework to introduce the acyloxyl group onto heterocyclic compounds with excellent regioselectivity. The developed method offers a wide substrate and excellent functional group tolerance.

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Section: Resultssupporting

confidence: 62%

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

Gupta

Kumar

et al. 2019

ChemistrySelect

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“…Palladium(II)‐catalyzed selective acetoxylation of morpholinones was reported by Gaunt with coworkers. [ 67 ] The reaction was carried out in AcOH/Ac 2 O solvent system with PhI(OAc) 2 as oxidant, yielding highly functionalized aminoalcohol derivatives 87 (Scheme 13). The mechanism of this C‐H acetoxylation was proposed based on detailed DFT calculations and kinetic measurements.…”

Section: Transition Metal Catalyzed Acyloxylationsmentioning

confidence: 99%

Recent progress in catalytic acyloxylation of C(sp³)‐H bonds

Antonov

Bryliakov

2022

Applied Organom Chemis

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Herewith, recent progress in the transition metal catalyzed, as well as metal‐free and electrochemical selective acyloxylations of C(sp3)‐H bonds is surveyed. The corresponding modifications of different substrate types such as amines, amides, oximes, aminoacids, nitrogen‐containing heterocycles, olefins, carbonyl compounds, carboxylic acids, and acetals are covered, focusing on their synthetic potential. Correlations between the nature of the catalyst, oxidant, additives, conditions, and the acyloxylation regio‐ and chemoselectivity, are revealed, and available mechanistic details are discussed briefly. The time span of the review is 2015 to present time.

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“…It was proposed that the MICA group first complexes with Pd II , which is subsequently oxidized to Pd IV by PhI (OAC) 2 . The resulting complex proceeded through an octahedral transition state that exhibited an out-of-plane conformation favoring acetoxylation at the methyl branch of Ile ( Buettner et al, 2019 ; Shabani et al, 2021 ). The resulting acetoxyl group was directly displaced by benzylthiol to form 59 in the presence of an indium triiodide catalyst ( Nishimoto et al, 2012 ).…”

Section: Synthesis Of Thiolated/selenylated Amino Acidsmentioning

confidence: 99%

Synthetic Thiol and Selenol Derived Amino Acids for Expanding the Scope of Chemical Protein Synthesis

et al. 2022

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Cells employ post-translational modifications (PTMs) as key mechanisms to expand proteome diversity beyond the inherent limitations of a concise genome. The ability to incorporate post-translationally modified amino acids into protein targets via chemical ligation of peptide fragments has enabled the access to homogeneous proteins bearing discrete PTM patterns and empowered functional elucidation of individual modification sites. Native chemical ligation (NCL) represents a powerful and robust means for convergent assembly of two homogeneous, unprotected peptides bearing an N-terminal cysteine residue and a C-terminal thioester, respectively. The subsequent discovery that protein cysteine residues can be chemoselectively desulfurized to alanine has ignited tremendous interest in preparing unnatural thiol-derived variants of proteogenic amino acids for chemical protein synthesis following the ligation-desulfurization logic. Recently, the 21st amino acid selenocysteine, together with other selenyl derivatives of amino acids, have been shown to facilitate ultrafast ligation with peptidyl selenoesters, while the advancement in deselenization chemistry has provided reliable bio-orthogonality to PTMs and other amino acids. The combination of these ligation techniques and desulfurization/deselenization chemistries has led to streamlined synthesis of multiple structurally-complex, post-translationally modified proteins. In this review, we aim to summarize the latest chemical synthesis of thiolated and selenylated amino-acid building blocks and exemplify their important roles in conquering challenging protein targets with distinct PTM patterns.

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Mechanistic investigation into the C(sp³)–H acetoxylation of morpholinones

Abstract: The study of a selective palladium(ii)-catalyzed C(sp3)–H acetoxylation reaction on a class of cyclic alkyl amines is reported.

Cited by 27 publications

References 32 publications

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

Recent progress in catalytic acyloxylation of C(sp³)‐H bonds

Synthetic Thiol and Selenol Derived Amino Acids for Expanding the Scope of Chemical Protein Synthesis

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Mechanistic investigation into the C(sp3)–H acetoxylation of morpholinones

Abstract: The study of a selective palladium(ii)-catalyzed C(sp3)–H acetoxylation reaction on a class of cyclic alkyl amines is reported.

Cited by 27 publications

References 32 publications

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

N‐Directed Pd‐Catalyzed Direct ortho‐Acetoxylation and ortho‐tert‐Butoxylation of 2‐Phenyl‐4H‐benzo[d][1,3]oxazin‐4‐ones via C‐H Activation

Recent progress in catalytic acyloxylation of C(sp3)‐H bonds

Synthetic Thiol and Selenol Derived Amino Acids for Expanding the Scope of Chemical Protein Synthesis

Contact Info

Product

Resources

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Mechanistic investigation into the C(sp³)–H acetoxylation of morpholinones

Recent progress in catalytic acyloxylation of C(sp³)‐H bonds