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Fullerene C60 promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary N-alkylbenzylamines.


ABSTRACT: C60-promoted photoaddition reactions of both trimethylsilyl- and a variety of alkyl group containing tertiary benzylamines (i.e., N-α-trimethylsilyl-N-alkylbenzylamines) with dimethyl acetylenedicarboxylate (DMAD) were carried out to explore the synthetic utility of trimethylsilyl group containing tertiary amines as a substrate in the photochemical hydroamination reactions with dimethyl acetylenedicarboxylate (DMAD). The results showed that photoreactions of all the trimethylsilyl containing N-alkylbenzylamines with DMAD, under an O2-purged environment, produced non-silyl containing enamines efficiently through a pathway involving addition of secondary amines to DMAD, the former of which are produced by hydrolytic cleavage of in situ formed iminium ions. Exceptionally, five-membered N-heterocyclic rings, pyrroles, could be produced competitively in photoreaction of bulky alkyl (i.e., tert-butyl) group substituted benzylamines through a pathway involving 1,3-dipolar cycloaddition of azomethine ylides to DMAD. Furthermore, C60-sensitized photochemical reactions of non-silyl containing benzylamines with DMAD under oxygenated conditions took place in a less efficient and non-regioselective manner to produce enamine photoadducts. The observations made in this study show that regioselectivity of C60-promoted photochemical reactions of N-α-trimethylsilyl-N-alkylbenzylamines, leading to formation of secondary amines, can be controlled by the presence of the trimethylsilyl group, and that these trimethylsilyl containing tertiary amines can serve as a precursor of secondary amines for hydroamination reactions with a variety of electron deficient acetylenes.

SUBMITTER: Lim SH 

PROVIDER: S-EPMC8694821 | biostudies-literature | 2021 Feb

REPOSITORIES: biostudies-literature

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Fullerene C<sub>60</sub> promoted photochemical hydroamination reactions of an electron deficient alkyne with trimethylsilyl group containing tertiary <i>N</i>-alkylbenzylamines.

Lim Suk Hyun SH   Jang Hannara H   Cho Dae Won DW  

RSC advances 20210203 11


C<sub>60</sub>-promoted photoaddition reactions of both trimethylsilyl- and a variety of alkyl group containing tertiary benzylamines (<i>i.e.</i>, <i>N</i>-α-trimethylsilyl-<i>N</i>-alkylbenzylamines) with dimethyl acetylenedicarboxylate (DMAD) were carried out to explore the synthetic utility of trimethylsilyl group containing tertiary amines as a substrate in the photochemical hydroamination reactions with dimethyl acetylenedicarboxylate (DMAD). The results showed that photoreactions of all t  ...[more]

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