Recent progress in catalytic acyloxylation of C(sp<sup>3</sup>)‐H bonds

Antonov, A. A.; Bryliakov, Konstantin P.

doi:10.1002/aoc.6499

Cited by 9 publications

(4 citation statements)

References 125 publications

(192 reference statements)

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“…The Pd(II)‐catalyzed reaction of 4 a with n− BuI did not yield the alkylated product 26 e (Scheme 11). Additionally, we also performed the Pd(II)‐catalyzed ABTD‐aided sp 3 γ‐ C−H acetoxylation [1z] of the methyl group of substrate 9 a using PhI(OAc) 2 as an oxidant in toluene at 110 °C for 24 h [1z,2] . This reaction afforded the γ‐ C(sp 3 )−H acetoxylated 3‐thiophene‐2‐carboxamide derivative 27 in 65% yield (Scheme 11).…”

Section: Resultsmentioning

confidence: 99%

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

2022

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Expanding the availability, scope, and limitations of directing groups (DGs) for executing the site-selective CÀ H activation and functionalization and substrate scope development are valuable efforts. This paper reports the scope and extension of the utility of the 4-amino-2,1,3-benzothiadiazole (ABTD) directing group in the Pd(II)-catalyzed arylation of remote sp 2 /sp 3 γ-CÀ H bonds of aromatic carboxamides and sp 3 β-CÀ H bonds of amino acid carboxamides. The performance of the ABTD DG in the arylation of remote γ-CÀ H bonds of carboxamides and sp 3 β-CÀ H bonds of amino acid carboxamides was compared with other known DGs. For example, we have observed that the mono arylation of the methyl sp 3 β-CÀ H bonds of alanine carboxamide possessing the ABTD DG with iodopyridine yielded the pyridylalanine derivative. Conversely, the same reaction using 8-AQ DG did not yield the expected pyridylalanine derivative. Furthermore, 2,1,3-benzothiadiazole moiety-containing compounds are an important class of molecules in materials chemistry and medicinally relevant molecules. While this work reveals the utility of ABTD as the DG in the Pd(II)-catalyzed CÀ H arylation of carboxamides including amino acid derivatives. On the other hand, indirectly the process of ABTD-aided CÀ H arylation reactions has enabled to accomplish the synthesis of a library of 2,1,3-benzothiadiazole moiety containing new carboxamides.

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Section: Resultsmentioning

confidence: 99%

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

2022

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“…Various oxidants, such as PhI(OAc) 2 , oxone, K 2 S 2 O 8 , t BuOOAc, and so on, have been used in transition-metal-catalyzed C – H activation reactions to construct C – O bonds (Scheme a) . Among these methods for C – O bond formation, the majority of them focused on C – H acyloxylation, alkoxylation, and hydroxylation . Nonetheless, other types of C – O functionalizations, such as nitrooxylation and sulfonyloxylation, were rarely reported …”

Section: Introductionmentioning

confidence: 99%

Palladium-Catalyzed C(sp³)–H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants

Liu,

Gao,

Xue

et al. 2024

J. Org. Chem.

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Here we report the palladium-catalyzed β-C(sp 3 )−H nitrooxylation of aliphatic carboxamides using a modified quinoline auxiliary. Notably, Al(NO 3 ) 3 •9H 2 O was used as a nitrate source as well as a practical oxidant. The 5-chloro-8-aminoquinoline auxiliary was nitrated in situ during the reaction, which may enhance its directing ability and help its removal. The reaction has a broad substrate scope with a variety of aliphatic carboxamides. The multiple substituted auxiliary can be easily removed and recovered. Two C−Hinsertion palladacycle intermediates were isolated and characterized to elucidate the mechanism.

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“…Consequently, the development of catalytic strategies for C–O bond-formation has become an increasingly important research subject in organic synthesis. The past decades have witnessed tremendous advances in the implementation of transition-metal-catalyzed cross-coupling methods for constructing C–O bonds with diverse O -nucleophiles, − including the emerging catalytically enantioselective hydroalkoxylation of multiple C–C bonds . Moreover, because of its distinct radical-involved pathways, the Kharasch–Sosnovsky-type allylic oxidation of alkenes provides a versatile and promising alternative method for forming C–O bonds though it is still largely undeveloped.…”

Section: Introductionmentioning

confidence: 99%

Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

2023

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The C−O bond is ubiquitous in biologically active molecules, pharmaceutical agents, and functional materials, thereby making it an important functional group. Consequently, the development of C−O bond-forming reactions using catalytic strategies has become an increasingly important research topic in organic synthesis because more conventional methods involving strong base and acid have many limitations. In contrast to the ionic-pathway-based methods, copper-promoted radical-mediated C− O bond formation is experiencing a surge in research interest owing to a renaissance in free-radical chemistry and photoredox catalysis. This Perspective highlights and appraises state-of-the-art techniques in this burgeoning research field. The contents are organized according to the different reaction types and working models.

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

Cited by 9 publications

References 125 publications

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

Palladium-Catalyzed C(sp³)–H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants

Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

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

Cited by 9 publications

References 125 publications

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

Utility of 4‐Amino‐2,1,3‐benzothiadiazole Directing Group in the Pd(II)‐catalyzed Arylation of γ‐C−H Bonds of Carboxamides and β‐C‐H Bonds of Amino Acid Carboxamides

Palladium-Catalyzed C(sp3)–H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants

Emerging Trends in Copper-Promoted Radical-Involved C–O Bond Formations

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Product

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

Palladium-Catalyzed C(sp³)–H Nitrooxylation of Aliphatic Carboxamides with Practical Oxidants