10335-95-2Relevant articles and documents
DIALKYL ACYLPHOSPHONATES: A NEW ACYLATING AGENT OF ALCOHOLS
Sekine, Mitsuo,Kume, Akiko,Hata, Tsujiaki
, p. 3617 - 3620 (1981)
Diethyl benzoylphosphonate (1) underwent facile benzoylation of alcohols in the presence of DBU.Reactions of diols containing primary and secondary hydroxyl groups with 1 gave predominantly monobenzoates in which primary hydroxyl groups were highly selectively benzoylated.Related acylations were also described.
Nonenzymatic kinetic resolution of 1,2-diols catalyzed by an organotin compound
Iwasaki, Fumiaki,Maki, Toshihide,Nakashima, Waka,Onomura, Osamu,Matsumura, Yoshihiro
, p. 969 - 972 (1999)
(matrix presented) A new nonenzymatic kinetic resolution method of 1,2-diols 1 using chiral organotin catalyst A with benzoyl chloride was developed. A remarkable effect due to an inorganic base such as sodium carbonate and a small portion of water on the ee of the main products 2 was observed. The reaction showed high enantio-and chemoselectivities to 1,2-diols 1.
An inexpensive catalyst, Fe(acac)3, for regio/site-selective acylation of diols and carbohydrates containing a 1,2-: Cis -diol
Lv, Jian,Ge, Jian-Tao,Luo, Tao,Dong, Hai
, p. 1987 - 1991 (2018)
This work describes the [Fe(acac)3] (acac = acetylacetonate)-catalyzed, regio/site-selective acylation of 1,2- and 1,3-diols and glycosides containing a cis-vicinal diol. The iron(iii) catalysts initially formed cyclic dioxolane-type intermediates with substrates between the iron(iii) species and vicinal diols, and the efficient and selective acylation of one hydroxyl group was subsequently achieved by adding acylation reagents in the presence of diisopropylethylamine (DIPEA) under mild conditions. This reaction generally produced high selectivities and highly isolated yields with the same protection pattern as that achieved with dibutyl tinoxide-mediated schemes.
An Efficient Method for the Chemoselective Preparation of Benzoylated 1,2-Diols from Epoxides
Khalafi-Nezhad,Soltani Rad,Khoshnood
, p. 2552 - 2558 (2003)
A very efficient and highly regioselective ring-opening reaction of epoxides with benzoic acid and its derivatives in the presence of cat. amount of tetrabutylammonium bromide (TBAB) in anhydrous acetonitrile has been developed. This effective method is useful for the preparation of selectively protected diols as precursor for many organic syntheses such as those of acyclic nucleosides and other synthetic purposes. The advantages of this method are efficiency, selectivity, low cost, and the applicability in large-scale synthesis of β-benzoyloxyalkanols.
A new convenient method for selective monobenzoylation of diols
Maki, Toshihide,Iwasaki, Fumiaki,Matsumura, Yoshihiro
, p. 5601 - 5604 (1998)
A new facile method for monoacylation of diols has been developed. A variety of cyclic and acyclic diols, in particular 1,2-diols, was selectively monobenzoylated in good yields by their reaction with benzoyl chloride in the presence of a catalytic amount of dimethyltin dichloride and inorganic bases.
Direct esterification of carboxylic acids with alcohols catalyzed by Iron(III) acetylacetonate complex
Weng, Shiue-Shien,Chen, Fong-Kuang,Ke, Chih-Shueh
, p. 2615 - 2621 (2013)
Direct condensation of carboxylic acids and alcohols with electronic, steric, and functional group variations was carried out using the environmentally benign, moisture-stable, inexpensive, and recoverable iron(III) acetylacetonate [Fe(acac)3] as catalyst (5 mol%). This iron salt efficiently catalyzed the esterification of several primary and secondary alcohols in refluxing xylene, without the need for a dehydration reagent. The chemoselectivity of the proposed protocol was demonstrated by the selective esterification of primary alcohol functionality in racemic 1-phenylethane-1,2- diol with benzoic acid. The esterification was also applicable to unmasked α-hydroxyacid, guasiaromatic, heterocyclic, and N-protected amino acids. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
Size-Induced Inversion of Selectivity in the Acylation of 1,2-Diols
Mayr, Stefanie,Zipse, Hendrik
, p. 18084 - 18092 (2021/12/02)
Relative rates for the Lewis base-catalyzed acylation of aryl-substituted 1,2-diols with anhydrides differing in size have been determined by turnover-limited competition experiments and absolute kinetics measurements. Depending on the structure of the anhydride reagent, the secondary hydroxyl group of the 1,2-diol reacts faster than the primary one. This preference towards the secondary hydroxyl group is boosted in the second acylation step from the monoesters to the diester through size and additional steric effects. In absolute terms the first acylation step is found to be up to 35 times faster than the second one for the primary alcohols due to neighboring group effects.
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.
Method for high selectivity acylation protection on hydroxyl through catalyzing by stannous chloride
-
Paragraph 0076-0077, (2020/09/16)
The invention belongs to the technical field of chemical synthesis of fine chemicals and sugar, and discloses a method for high selectivity acylation protection on hydroxyl through catalyzing by stannous chloride. The method comprises the steps of dissolv
Stannous chloride as a low toxicity and extremely cheap catalyst for regio-/site-selective acylation with unusually broad substrate scope
Dong, Hai,Feng, Guang-Jing,Luo, Tao,Lv, Jian,Yu, Jian-Cheng
supporting information, p. 6936 - 6942 (2020/11/09)
This work reports stannous chloride (SnCl2)-catalyzed regio-/site-selective acylation with unusually broad substrate scope. In addition to 1,2- and 1,3-diols and glycosides containing cis-vicinal diol, the substrate scope also includes glycosides without cis-vicinal diol. For such a substrate scope, usually, only methods using stoichiometric amounts of organotin reagents can lead to the same protection pattern with high selectivities and highly isolated yields (84-97% in most cases). Therefore, SnCl2, as a low toxicity and extremely cheap reagent, should be the best catalyst for regio-/site-selective acylation compared with any previously reported reagents. This journal is
