Aromatic Chemistry in the Excited State: Facilitating Metal‐Free Substitutions and Cross‐Couplings

Liu, Wenbo; Li, Jianbin; Huang, Chun-Hong; Li, Chao‐Jun

doi:10.1002/ange.201909138

Cited by 7 publications

(2 citation statements)

References 55 publications

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“…Therefore, a catalytic cross-dehydrogenative Minisci alkylation without stoichiometric chemical oxidants is long-sought-after 39 . Our group has a long-term interest in the arene functionalisation, which was facilitated by the excited aromatics under catalyst-free conditions [42][43][44][45][46][47] . Recently, we documented a simple and clean Minisci alkylation reaction via formal dehydrative coupling of heteroarenes with alcohols.…”

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confidence: 99%

A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

Huang

2021

Nat Commun

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Hydrogen atom abstraction (HAT) from C(sp3)–H bonds of naturally abundant alkanes for alkyl radical generation represents a promising yet underexplored strategy in the alkylation reaction designs since involving stoichiometric oxidants, excessive alkane loading, and limited scope are common drawbacks. Here we report a photo-induced and chemical oxidant-free cross-dehydrogenative coupling (CDC) between alkanes and heteroarenes using catalytic chloride and cobalt catalyst. Couplings of strong C(sp3)–H bond-containing substrates and complex heteroarenes, have been achieved with satisfactory yields. This dual catalytic platform features the in situ engendered chlorine radical for alkyl radical generation and exploits the cobaloxime catalyst to enable the hydrogen evolution for catalytic turnover. The practical value of this protocol was demonstrated by the gram-scale synthesis of alkylated heteroarene with merely 3 equiv. alkane loading.

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confidence: 99%

A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

Huang

2021

Nat Commun

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135

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“…Its success would represent a significant step forward to simplify tertiary amines synthesis from bench-stable and commercially cheap nitroarenes. As our continual interests in the highly efficient organic transformation of carboxylic acids 37 – 40 , we dedicate to developing a catalytic decarboxylative C-N coupling 41 – 48 from carboxylic acids.…”

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confidence: 99%

Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism

Wang

et al. 2022

Nat Commun

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Aromatic tertiary amines are one of the most important classes of organic compounds in organic chemistry and drug discovery. It is difficult to efficiently construct tertiary amines from primary amines via classical nucleophilic substitution due to consecutive overalkylation. In this paper, we have developed a radical tandem C-N coupling strategy to efficiently construct aromatic tertiary amines from commercially available carboxylic acids and nitroarenes. A variety of aromatic tertiary amines can be furnished in good yields (up to 98%) with excellent functional group compatibility under mild reaction conditions. The use of two different carboxylic acids also allows for the concise synthesis of nonsymmetric aromatic tertiary amines in satisfactory yields. Mechanistic studies suggest the intermediacy of the arylamine–(TPP)Fe(III) species and might provide a possible evidence for an SH2 (bimolecular homolytic substitution) pathway in the critical C-N bond formation step.

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Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

Huang

2022

Angewandte Chemie

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The simple and efficient conversion of carbonyl compounds into functionalized alkanes via deoxygenation is highly enabling in chemical synthesis. This Review covers the recent methodology development in carbonyl and carboxyl deoxygenative functionalizations, highlighting some representative and significant contributions in this field. These advances are categorized based on the reactivity patterns of some oxygenated feedstock compounds, including aldehydes, ketones and carboxylic acids. Four types of reactive intermediates arising from aldehydes and ketones during the deoxygenation, namely, bis‐electrophiles, carbenoids, bis‐nucleophiles and alkyl radical equivalents, are presented, while the carboxylic acids mainly behave as tris‐electrophiles when deoxygenated. In each subcategory, selected examples are organized according to the type of bond formation and discussed from a generalized mechanistic perspective.

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Aromatic Chemistry in the Excited State: Facilitating Metal‐Free Substitutions and Cross‐Couplings

Cited by 7 publications

References 55 publications

A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

A cross-dehydrogenative C(sp3)−H heteroarylation via photo-induced catalytic chlorine radical generation

Decarboxylative tandem C-N coupling with nitroarenes via SH2 mechanism

Deoxygenative Functionalizations of Aldehydes, Ketones and Carboxylic Acids

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