Oxidative rearrangement of 1,1-disubstituted alkenes to ketones

Feng, Qiang; Wang, Qian; Zhu, Jieping

doi:10.1126/science.adg3182

Cited by 24 publications

(12 citation statements)

References 79 publications

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“…These results suggest that an alternative Pd II /Pd IV catalytic cycle is more suitable for the present reaction, consistent with our initial design (see the Supporting Information for details) . No reaction took place between TBHP and Pd(TFA) 2 at room temperature, as evidenced by 19 F nuclear magnetic resonance (NMR) spectra, suggesting that a Pd IV species is formed only after the generation of an alkyl-Pd II intermediate (Scheme b) . When N -methyl- p -toluidine 4a was subjected to the standard reaction conditions for 120 min, the β-arylamino - γ-lactone product 5a was obtained in 36% yield along with a trace amount of β-lactone product 8 (Scheme c).…”

supporting

confidence: 83%

Access to Amino Lactones through Palladium-Catalyzed Oxyamination with Aromatic Amines as the Nitrogen Source

Liu

Tan

et al. 2023

ACS Catal.

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Although the synthesis of amino lactones with various nitrogen sources has achieved great success, variants focused on aromatic amine counterparts still remain elusive. Herein, we communicate the intermolecular oxyamination reaction of aromatic amines and unactivated alkenyl carbonyl compounds under palladium catalysis. In the reaction, both primary and second aromatic amines yield the corresponding β-arylamino-γ-lactones efficiently. A key step in this process involves a Pd II /Pd IV catalytic cycle incorporating a 1,2-(C−N)/(C−O) dyotropic rearrangement. This reaction demonstrates mild reaction conditions and good functional group compatibility.

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supporting

confidence: 83%

Access to Amino Lactones through Palladium-Catalyzed Oxyamination with Aromatic Amines as the Nitrogen Source

Liu

Tan

et al. 2023

ACS Catal.

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“…This reaction paradigm introduces transformations in which adjacent carbon atoms undergo complementary oxidation level transfers, obviating the need for single carbon atom oxidation level changes thereby curtailing nonstrategic and lengthy sequences of redox manipulations . Such a conceptual framework has been encapsulated elegantly in a seminal report from Dong and co-workers of a net redox-neutral sequence transposing ketone functionality and, more recently, in an oxidative rearrangement of 1,1-disubstituted alkenes to ketones, reported by Zhu …”

mentioning

confidence: 99%

1,2-Redox Transpositions of Tertiary Amides

Shennan,

Sánchez-Alonso,

Rossini

et al. 2023

J. Am. Chem. Soc.

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Reactions capable of transposing the oxidation levels of adjacent carbon atoms enable rapid and fundamental alteration of a molecule's reactivity. Herein, we report the 1,2-transposition of the carbon atom oxidation level in cyclic and acyclic tertiary amides, resulting in the one-pot synthesis of 1,2-and 1,3-oxygenated tertiary amines. This oxidation level transfer was facilitated by the careful orchestration of an iridium-catalyzed reduction with the functionalization of transiently formed enamine intermediates. A novel 1,2-carbonyl transposition is described, and the breadth of this redox transposition strategy has been further explored by the development of aminoalcohol and enaminone syntheses. The diverse β-functionalized amine products were shown to be multifaceted and valuable synthetic intermediates, accessing challenging biologically relevant motifs.

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“…Such processes reform notoriously non-strategic and lengthy sequences of redox manipulations into highly choreographed "oxidation level dances" to deliver efficiently high-value building blocks and intermediates. Such a conceptual framework has been encapsulated elegantly in a seminal report from Dong of a net redox-neutral sequence transposing ketone functionality (9) and, more recently, in an palladium-mediated oxidative rearrangement of 1,1-disubstituted alkenes to ketones, reported by Zhu (10).…”

mentioning

confidence: 99%

1,2-Redox Transpositions of Tertiary Amides

Shennan

Alonso

Dixon

2023

Preprint

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Reactions capable of transposing the oxidation levels of adjacent carbon atoms in organic molecules enable rapid and fundamental alteration of a molecule’s reactivity. Herein, we report the 1,2-transposition of carbon atom oxidation level in cyclic and acyclic tertiary amides, resulting in the one-pot synthesis of 1,2- and 1,3-oxygenated tertiary amines. This oxidation level transfer was facilitated by the careful orchestration of an iridium-catalyzed reduction with the functionalization of transiently-formed enamine intermediates. Remarkably, a novel 1,2-carbonyl transposition was observed when the commercial oxidant mCPBA was selected as the coupling partner. The scope of this transformation and the breadth of this redox transposition strategy has been explored and the diverse β-functionalized amine products were shown to be multi-faceted and valuable synthetic intermediates, accessing challenging biologically-relevant motifs.

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Oxidative rearrangement of 1,1-disubstituted alkenes to ketones

Cited by 24 publications

References 79 publications

Access to Amino Lactones through Palladium-Catalyzed Oxyamination with Aromatic Amines as the Nitrogen Source

Access to Amino Lactones through Palladium-Catalyzed Oxyamination with Aromatic Amines as the Nitrogen Source

1,2-Redox Transpositions of Tertiary Amides

1,2-Redox Transpositions of Tertiary Amides

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