From alkylarenes to anilines via site-directed carbon–carbon amination

Liu, Jianzhong; Qiu, Xu; Huang, Xiaoqiang; Luo, Xiaoling; Zhang, Cheng; Wei, Jialiang; Pan, Jun; Liang, Yujie; Zhu, Yuchao; Q, Qin; Song, Song; Jiao, Ning

doi:10.1038/s41557-018-0156-y

Cited by 112 publications

(65 citation statements)

References 48 publications

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“…[2] However, the C À C bond cleavage of unstrained aliphatic rings has long been viewed as an extremely challenging problem owing to the high CÀC bond dissociation energy. [3,4] One promising strategy to solve this problem is to take advantage of the high reactivity of oxygen radicals to facilitate the ring-opening by C À C bond cleavage. In this context, elegant methods have been developed based on the cycloalkoxy radical promoted ring opening.…”

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confidence: 99%

Deconstructive Oxygenation of Unstrained Cycloalkanamines

et al. 2020

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A deconstructive oxygenation of unstrained primary cycloalkanamines has been developed for the first time using an auto‐oxidative aromatization promoted C(sp3)−C(sp3) bond cleavage strategy. This metal‐free method involves the substitution reaction of cycloalkanamines with hydrazonyl chlorides and subsequent auto‐oxidative annulation to in situ generate pre‐aromatics, followed by N‐radical‐promoted ring‐opening and further oxygenation by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) and m‐cholorperoxybenzoic acid (mCPBA). Consequently, a series of 1,2,4‐triazole‐containing acyclic carbonyl compounds were efficiently produced. This protocol features a one‐pot operation, mild reaction conditions, high regioselectivity and ring‐opening efficiency, broad substrate scope, and is compatible with alkaloids, osamines, and peptides, as well as steroids.

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confidence: 99%

Deconstructive Oxygenation of Unstrained Cycloalkanamines

et al. 2020

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“…However, in most cases, such methods rely on the starting materials derived from non-renewable petroleum based chemicals (BTX, benzene, toluene, xylenes etc. ),2 in which extra pre-functionalization steps of arenes by nitration,3 halogenation4 and borylation5 are required to generate the corresponding aromatic nitro compounds, arylhalides and arylboron compounds in order to form primary anilines (Scheme 1a and b)1c,6. On the other hand, naturally abundant phenols, which constitute some of the main units of lignin bio-mass and are widely obtainable at very low cost from coal and cumene industrial processes, are often considered as the alternative renewable aromatic feedstocks 7.…”

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Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium

Qiu

et al. 2019

Chem. Sci.

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“…[24] Apart from phenols, anilines can also be obtained directly from lignin-model compounds. [25] In this regard, Jiao and co-workers [25] have discovered an elegant approach for the preparation of anilines via site-directed CÀ C bond cleavage of lignin-model compounds and subsequent amination to obtain anilines by using sodium azide (Scheme 5). Here, β-1 (8β-1 lignin-T and 8-β-1 lignin-E) and β-O-lignin model compounds, which are ubiquitous chemical linkages found in lignin spruce trees, were selectively cleaved and produced 4-methoxyaniline and 3,4-dimethoxy aniline in 40-53% yield (Scheme 5).…”

Section: Synthesis Of Amines From Lignin-derived Monomersmentioning

confidence: 99%

Synthesis of Functional Chemicals from Lignin‐derived Monomers by Selective Organic Transformations

et al. 2020

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The valorization of lignin and its model compounds represents a key technology applied for the production of lignin-monomers, which constitute as renewable feedstocks and intermediates for the synthesis of value-added chemicals and fuels as well as molecules related to life science applications. Hence, in addition to lignin-depolymerization, the effective utilization of lignin-derived feedstocks such as phenols, ethers, alcohols, ketones and aldehydes is also gaining significant importance. In this regard, number of methodologies has been developed on the utility of these feedstocks for the production of various functional chemicals. In this review, we summarize the valorization of lignin-derived feedstocks by amination, hydrogenation, dehydrogenation oxidation, carbonylation, and trifluoromethylation, hydrolysis reactions for the synthesis of amines, cyclohexanes, cyclohexanols, cyclohexanones, esters, ketones, cyclic ethers, trifluoromethylated compounds and heterocycles as well as pharmaceuticals and biomolecules.

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From alkylarenes to anilines via site-directed carbon–carbon amination

Cited by 112 publications

References 48 publications

Deconstructive Oxygenation of Unstrained Cycloalkanamines

Deconstructive Oxygenation of Unstrained Cycloalkanamines

Direct conversion of phenols into primary anilines with hydrazine catalyzed by palladium

Synthesis of Functional Chemicals from Lignin‐derived Monomers by Selective Organic Transformations

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