119740-88-4Relevant articles and documents
Directional migration method of benzoyl between hydroxyls based on sulfoacid catalysis
-
Paragraph 0094-0098, (2020/02/14)
The invention discloses a directional migration method of benzoyl between hydroxyls based on sulfoacid catalysis, and relates to the technical field of chemical synthesis. Specifically, under the catalysis condition of sulphonic acid, the migration of acyl groups of the benzoyl is selectively completed through via of an ortho-ester intermediate in a high region, the characteristics of the migration are shown as follows: two hydroxyls of 5-ortho-ester rings or 6-ortho-ester rings can be formed in space, and the benzoyl can be migrated from secondary hydroxyls or tertiary hydroxyls to primary hydroxyls, and can be migrated from upright-position secondary hydroxyls to flat-position hydroxyls. According to the directional migration method disclosed by the invention, the sulfoacid is used for promoting acyl functional groups in a substrate to generate a 1,2-migration reaction or 1,3-migration reaction, the whole synthesis reaction condition is mild, the operation is simple, and atoms are economic.
Regioselective Sulfonylation/Acylation of Carbohydrates Catalyzed by FeCl3 Combined with Benzoyltrifluoroacetone and Its Mechanism Study
Dong, Hai,Liu, Yu,Lv, Jian,Zhu, Jia-Jia
, p. 3307 - 3319 (2020/03/25)
A catalytic amount of FeCl3 combined with benzoyl trifluoroacetone (Hbtfa) (FeCl3/Hbtfa = 1/2) was used to catalyze sulfonylation/acylation of diols and polyols using diisopropylethylamine (DIPEA) or potassium carbonate (K2CO3) as a base. The catalytic system exhibited high catalytic activity, leading to excellent isolated yields of sulfonylation/acylation products with high regioselectivities. Mechanism studies indicated that FeCl3 initially formed [Fe(btfa)3] (btfa = benzoyl trifluoroacetonate) with twice the amount of Hbtfa under basic conditions in the solvent acetonitrile at room temperature. Then, Fe(btfa)3 and two hydroxyl groups of the substrates formed a five- or six-membered ring intermediate in the presence of the base. The subsequent reaction between the cyclic intermediate and a sulfonylation reagent led to the selective sulfonylation of the substrate. All key intermediates were captured in the high-resolution mass spectrometry assay, therefore demonstrating this mechanism for the first time.
Regioselective benzoylation of diols and carbohydrates by catalytic amounts of organobase
Lu, Yuchao,Hou, Chenxi,Ren, Jingli,Xin, Xiaoting,Xu, Hengfu,Pei, Yuxin,Dong, Hai,Pei, Zhichao
, (2016/07/06)
A novel metal-free organobase-catalyzed regioselective benzoylation of diols and carbohydrates has been developed. Treatment of diol and carbohydrate substrates with 1.1 equiv. of 1-benzoylimidazole and 0.2 equiv. of 1,8-diazabicyclo[5.4.0]undec-7-ene (DB