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Experimental and density functional theory studies on hydroxymethylation of phenylboronic acids with paraformaldehyde over a RhPPh 3 catalyst
Author(s) -
Wang Kuan,
Lan Jie,
He ZhenHong,
Cao Zhe,
Wang Weitao,
Yang Yang,
Liu ZhaoTie
Publication year - 2021
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/aoc.6104
Subject(s) - chemistry , paraformaldehyde , phenylboronic acid , catalysis , hydrolysis , density functional theory , aryl , combinatorial chemistry , organic chemistry , medicinal chemistry , computational chemistry , alkyl
The synthesis of benzyl alcohols (BAs) is highly vital for their wide applications in organic synthesis and pharmaceuticals. Herein, BAs was efficiently synthesized via hydroxymethylation of phenylboronic acids (PBAs) and paraformaldehyde over a simple RhPPh 3 catalyst combined with an inorganic base (NaOH). A variety of BAs with the groups of CH 3 − , CH 3 O − , Cl − , Br − , and so on were obtained with moderate to good yields, indicating that the protocol had a good universality. Density functional theory (DFT) calculations proposed the Hayashi‐type arylation mechanism involved the arylation step of PBA and Rh(OH)(PPh 3 ) 2 catalyst to form Rh(I)‐bound aryl intermediates and the hydrolysis step of Rh(I)‐bound aryl intermediates and HCHO to generate BA product (the rate‐determining step). The present route provides a valuable and direct method for the synthesis of BAs and expands the application range of paraformaldehyde.