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. 2024 Jun 10;366(11):2489-2494.
doi: 10.1002/adsc.202301505. Epub 2024 Apr 9.

n-Bu4NI/K2S2O8 Mediated Csp2-Csp2 Bond Cleavage - Transformylation from p-Anisaldehyde to Primary Amides

Xiaochen Liu  1   2 , Samual Hee  1   2 , Netanel G Sapir  1 , Alvin Li  1 , Jianbo Liu  1   2 , Yu Chen  1   2
Affiliations

n-Bu4NI/K2S2O8 Mediated Csp2-Csp2 Bond Cleavage - Transformylation from p-Anisaldehyde to Primary Amides

Xiaochen Liu et al. Adv Synth Catal. .

Abstract

n-Bu4NI/K2S2O8 mediated transformylation from p-anisaldehyde to primary amides is reported. The mechanistic studies suggest the reaction occurs via a single electron transfer pathway. Based on the DFT electronic structure calculations of various reaction pathways, the most plausible mechanism involves the formation of a phenyl radical cation and an arenium ion as the key intermediates. It represents the first example where p-anisaldehyde is employed as a formyl source via a non-metal mediated Csp2-Csp2 bond cleavage.

Keywords: Csp2-Csp2 bond cleavage; N-formyl imide; n-Bu4NI/K2S2O8 mediated; single electron transfer reaction; transformylation.

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Figures

Figure 1.
Figure 1.
Natural Products and Pharmaceutical Intermediates Synthesized via Formyl Imides.
Scheme 1.
Scheme 1.
n-Bu4NI/K2S2O8 Mediated Transformylation from p-Anisaldehyde to Benzamide on Gram Scale.
Scheme 2.
Scheme 2.
Control Experiments Carried Out for the Mechanism Study.
Scheme 3.
Scheme 3.
Proposed Mechanism for the n-Bu4NI/K2S2O8 Mediated Transformylation from p-Anisaldehyde to Primary Amides.
See this image and copyright information in PMC

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