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Chemoselective Epoxidation of Allyloxybenzene by Hydrogen Peroxide Over MFI‐Type Titanosilicate
Author(s) -
Kon Yoshihiro,
Nakashima Takuya,
Hong Dachao,
Ji Xinyi,
Osuga Ryota,
Ito Satoru,
Fujitani Tadahiro,
Sato Kazuhiko,
Yokoi Toshiyuki
Publication year - 2020
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.202000249
Subject(s) - chemistry , hydrogen peroxide , catalysis , yield (engineering) , chemoselectivity , solvent , lewis acids and bases , peroxide , reaction mechanism , organic chemistry , titanium , medicinal chemistry , polymer chemistry , materials science , metallurgy
The chemoselective synthesis of 2‐(phenoxymethyl)oxirane from allyloxybenzene is achieved with over 90 % yield in a sustainable reaction system using titanium‐substituted silicalite‐1 (TS‐1) as a catalyst, hydrogen peroxide (H 2 O 2 ) as an oxidant, and a mixture of MeOH/MeCN as a solvent at 40 °C. No acid‐catalyzed side reactions prompted by the Lewis acidity of the Ti active site in TS‐1 are observed. The TS‐1 catalyst can also promote the formation of oxiranes from various p ‐substituted allyloxybenzenes in good yields. The reaction mechanism is investigated through the reaction with other allyloxy compounds. The results, which are supported by DFT calculations, indicate that an active species of Ti peroxides formed from the reaction of TS‐1 with H 2 O 2 selectively oxidizes the allyloxybenzene to 2‐(phenoxymethyl)oxirane.