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Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes.

ABSTRACT: The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an ?-silylated amine substrate and a subsequent protodesilylation reaction that delivers linear hydroaminoalkylation products with high selectivity from simple alkyl-substituted alkenes. For that purpose, new titanium catalysts have been developed, which are able to activate the ?-C-H bond of more challenging ?-silylated amine substrates. In addition, a direct relationship between the ligand structure of the new catalysts and the obtained regioselectivity is described.

SUBMITTER: Warsitz M

PROVIDER: S-EPMC7756280 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature

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Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes.

Warsitz Michael M Doye Sven S

Chemistry (Weinheim an der Bergstrasse, Germany) 20201022 66

The regioselective conversion of alkyl-substituted alkenes into linear hydroaminoalkylation products represents a strongly desirable synthetic transformation. In particular, such conversions of N-methylamine derivatives are of great scientific interest, because they would give direct access to important amines with unbranched alkyl chains. Herein, we present a new one-pot procedure that includes an initial alkene hydroaminoalkylation with an α-silylated amine substrate and a subsequent protodesi ...[more]

PMID: 32643801

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Project description:Chemical oxidation with hydroxyl radical (HO•) and sulfate radical (SO4•-) is often used to treat water contaminated with aromatic compounds. Although oxidation of aromatics by these radicals has been studied for decades, the commonly accepted transformation pathway-sequential hydroxylation of the ring followed by ring cleavage and mineralization of the resulting products-does not account for the loss of the parent compound observed during the initial phase of the process. To assess the importance of pathways for aromatic compound oxidation that do not result in ring hydroxylation, we identified products formed after the initial reaction between HO• or SO4•- and benzene, toluene, ethylbenzene, and (BTEX) xylene isomers. We quantified products of ring hydroxylation and oxidation of alkyl substituents as well as a suite of ring-cleavage products, including acetaldehyde, formic acid, 6-, 7-, or 8-carbon oxoenals and oxodials. Other ring-cleavage products, which were most likely aldehydes and organic acids, were observed but not quantified. When SO4•- was used as the oxidant, aromatic organosulfates also were formed. Our results indicated that the initial phase of the oxidation process involves radical addition, hydrogen abstraction, or one-electron transfer to the ring followed by reaction with O2. The hydroxycyclohexadienylperoxy radical produced in this reaction can eliminate hydroperoxyl radical (HO2•) to produce a phenolic compound or it can rearrange to form a bicyclic peroxy intermediate that subsequently undergoes ring cleavage. Hydroxylation of the ring and oxidation of the alkyl substituent accounted for approximately 15-40% of the reacted mass of the parent compound. Ring-cleavage products for which quantification was possible accounted for approximately 2 to 10% of the reacted mass. Our results raise concerns about the formation of toxic ring-cleavage products during the initial stage of oxidation whenever HO• or SO4•- is used for the treatment of water containing benzene or alkylbenzenes.

Dataset Information

Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes.

Publications

Linear Hydroaminoalkylation Products from Alkyl-Substituted Alkenes.

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