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Ruthenium‐Catalyzed Aminomethylation and Methylation of Phenol Derivatives Utilizing Methanol as the C 1 Source
Author(s) -
Kim Seoksun,
Hong Soon Hyeok
Publication year - 2017
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201601117
Subject(s) - chemistry , iminium , phenol , catalysis , ruthenium , formamide , methanol , dehydrogenation , reagent , organic chemistry , combinatorial chemistry , photochemistry
A reaction involving ortho ‐aminomethylation of phenol was developed via ruthenium‐catalyzed dehydrogenation of methanol, an environmentally benign C 1 building block, without the use of reactive reagents. The reaction was successfully applied to a range of substrates. When naphthol was employed instead of phenol, only methylation was observed. On the basis of various mechanistic studies, we propose that formamide barely participates in the reaction, which mainly occurs through an iminium cation intermediate. The difference in the reactivities of phenol and naphthol is attributable to stronger basicity of naphtholate as a conjugate base owing to its lower aromaticity. Plausible reaction pathways were proposed for both reactions.