- An efficient metal-free oxidative esterification and amination of benzyl C-H bond
-
An esterification and amination of benzylic C-H bonds was developed by using 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) under metal- and iodide-free conditions. Both carboxylic acids and amines could be used as ideal coupling partners for the oxidati
- Liu, Saiwen,Chen, Ru,He, Guowen,Zhang, Jin
-
-
- Making Carbonyls of Amides Nucleophilic and Hydroxyls of Alcohols Electrophilic Mediated by SO2F2 for Synthesis of Esters from Amides
-
We discovered that with the promotion of sulfuryl fluoride, the carbonyl groups of amides performed as nucleophiles while the hydroxyl groups of alcohols were activated to functionalize as electrophiles. This study displayed that the amide C-N bonds could be easily cleaved with delicate nucleophiles to form the ester C-O bonds at room temperature without using transition metals. The broad substrate scope and excellent functional group compatibility were proved with 44 examples in up to 99% yields.
- Fang, Wan-Yin,Zha, Gao-Feng,Qin, Hua-Li
-
supporting information
p. 8657 - 8661
(2019/10/17)
-
- Bioinspired Metal-Free Formal Decarbonylation of α-Branched Aliphatic Aldehydes at Ambient Temperature
-
A sequence of a Baeyer–Villiger oxidation and a Lewis acid-promoted reduction of the resulting formate with Et3SiH enabled the metal-free formal decarbonylation of tertiary and secondary aliphatic aldehydes. The new methodology mimics the biosynthetic decarbonylation pathway through oxidative C?C bond cleavage rather than the C(O)?H bond activation known from conventional Tsuji–Wilkinson-type reactions. The substrate scope is complementary to existing transition-metal-catalyzed protocols.
- Richter, Sven C.,Oestreich, Martin
-
supporting information
p. 8508 - 8512
(2019/06/04)
-
- Palladium-Catalyzed Carbonylative Synthesis of Benzyl Benzoates Employing Benzyl Formates as Both CO Surrogates and Benzyl Alcohol Sources
-
An efficient and convenient palladium-catalyzed carbonylation reaction for the synthesis of benzyl benzoates from aryl bromides has been developed. Benzyl formates have been explored as a new type of efficient and useful CO sources and also reaction partners. A wide range of benzyl benzoates was obtained in good to excellent yields.
- Lai, Ming,Qi, Xinxin,Wu, Xiao-Feng
-
supporting information
p. 3776 - 3778
(2019/06/24)
-
- Method for preparing formate-type compound
-
The invention discloses a method for preparing a formate-type compound. The method comprises the following steps of: adopting an alcohol-type compound and 1,3-dihydroxyacetone as reaction raw materials, and under the existence of a composite catalyst and an oxidant, reacting for 2-48 hours in a reaction medium in a reactor at a reaction temperature of 25-100 DEG C so as to obtain the formate-typecompound. The method disclosed by the invention is simple, and is mild in reaction condition, and by the method, a target product can be obtained by low cost and high yield; the used catalyst has highcatalytic activity, and is easily separated from a reaction system to be repeatedly used; the whole process is environment-friendly, and the reaction raw material (1,3-dihydroxyacetone) is easily converted from a side product (glycerol) of biodiesel, so that the utilization of the glycerol is promoted.
- -
-
Paragraph 0039; 0047; 0048
(2018/07/30)
-
- N-Heterocyclic Carbene Catalyzed Transformylation
-
The N-heterocyclic carbene (NHC) catalyzed transformylation has been developed for the conversion of 1°, 2°, and 3° alcohols to the corresponding formates. The reaction employs low catalyst loadings and methyl formate as the formyl transfer reagent. The scope of the reaction is broad with 23 examples reported with good yields (59-96%). The reaction is insensitive to common nitrogen and oxygen protecting groups and can be achieved in the presence of a number of heterocycles.
- Fernando, Jared E. M.,Levens, Alison,Moock, Daniel,Lupton, David W.
-
p. 3505 - 3510
(2017/07/27)
-
- Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions
-
Herein, formylation of structurally different amines and alcohols with ethyl formate was carried out in the presence of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)-encapsulated Fe3O4 nanoparticles as a heterogeneous, recyclable, and greatly efficient catalyst; this method provided the corresponding N-formyl compounds in good to excellent yields under solvent-free conditions. The magnetically catalytic system was recovered, by-passing the time-consuming filtration operation using an external magnet device. This procedure also increases the purity of the product and promises economic and ecological advantages. Furthermore, the recovery and reuse of the catalyst was demonstrated five times without detectable loss in the activity.
- Taheri, Sepideh,Veisi, Hojat,Hekmati, Malak
-
p. 5075 - 5081
(2017/07/11)
-
- Tribromoisocyanuric acid (TBCA) as a mild and metal free catalyst for the acetylation and formylation of hydroxyl groups under solvent free conditions
-
A convenient approach for acetylation and formylation of various types of alcohols and phenols with acetic anhydride and formic acid in the presence of Tribromoisocyanuric acid (TBCA) as catalyst is reported. The reactions were carried out under solvent-free condition and in good to high yields at room temperature. This present method is featured with relatively mild reaction conditions, simple operation, broad substrate scope, clean work-up, short reaction times, good to high yields, excellent selectivity and also avoids tedious purifications and the use of toxic reagents.
- Hekmatian, Zahra,Khazaei, Ardeshir
-
p. 1565 - 1570
(2016/01/26)
-
- Tribromo melamine as novel and versatile catalyst for the formylation and acetylation of alcohols
-
Tribromo melamine has been found to be an efficient and green organocatalyst for the acetylation and formylation reactions of alcohols with acetic anhydride and ethyl formate at room temperature and under mild reaction conditions.
- Hajjami, Maryam,Ghorbani-Choghamarani, Arash,Karamshahi, Zahra,Norouzi, Masoomeh
-
p. 260 - 263
(2014/03/21)
-
- Remarkable improvement achieved by imidazole derivatives in ruthenium-catalyzed hydroesterification of alkenes using formates
-
Imidazole derivatives are revealed to be effective ligands in the Ru-catalyzed hydroesterification of alkenes using formates, affording one-carbonelongated esters in high yields. Further, intramolecular hydroesterification was successfully performed to give lactones for the first time. Imidazole derivatives can contribute to promote the reaction as well as to suppress the undesired decarbonylation of formate. Toxic CO gas, a directing group, and large excess alkenes are not required.
- Konishi, Hideyuki,Muto, Takashi,Manabe, Kei,Ueda, Tsuyoshi
-
supporting information
p. 4722 - 4725,4
(2012/12/12)
-
- Formylation of alcohol with formic acid under solvent-free and neutral conditions catalyzed by free I2 or I2 generated in situ from Fe(NO3)3·9H2O/NaI
-
Different alcohols were formylated by formic acid under solvent-free conditions in the presence of iodine as the catalyst with good-to-high yields at room temperature. I2 generated in situ from Fe(NO3) 3·9H2O/NaI also catalyzed the formylation of the alcohols under solvent-free conditions. This gives a green and efficient reaction at room temperature, in which the use of toxic and corrosive molecular I2 is avoided.
- Amin, Rostami,Ardeshir, Khazaei,Heidar Ali, Alavi-Nik,Zahra, Toodeh-Roosta
-
experimental part
p. 60 - 64
(2011/10/08)
-
- N,N′-dibromo-N,N′-1,2-ethanediylbis(benzene sulfonamide) as an efficient catalyst for acetylation and formylation of alcohols under mild conditions
-
An efficient method for the acylation and formylation of alcohols and phenols by using an acylating/formylating agent (acetic anhydride and formic acid) in the presence of a catalytic amount of N,N′-dibromo-N,N′-1, 2-ethanediylbis(benzene sulfonamide) under mild and solvent-free conditions at room temperature in good to excellent yields is described. The use of protic acids and metal Lewis acids is avoided.
- Khazaei, Ardeshir,Rostami, Amin,Rosta, Zahra,Alavi, Ali
-
experimental part
p. 181 - 186
(2010/04/05)
-
- P-Toluenesulfonyl chloride as a new and effective catalyst for acetylation and formylation of hydroxyl compounds under mild conditions
-
The catalytic application of p-toluenesulfonyl chloride for efficient acetylation of various types of alcohols and phenols with acetic anhydride in solvent-free conditions is reported. Also structurally diverse alcohols were formylated using formic acid based on the use of catalytic amount of p-toluenesulfonyl chloride under solvent-free condition. The reactions were carried out in short reaction time and in good to excellent yields at room temperature.
- Khazaei, Ardeshir,Rostami, Amin,Mantashlo, Fatemeh
-
experimental part
p. 1430 - 1434
(2011/10/08)
-
- Highly efficient formylation of alcohols, thiols and aniline derivatives by a heterogeneous (HCOOH/SiO2) system under microwave irradiation and solvent-free conditions
-
A simple, rapid and efficient microwave-assisted procedure for the formylation of aniline derivatives and alcohols, using a heterogeneous (HCOOH/SiO2) system under solvent-free conditions is reported. The method is applied to a set of amines, alcohols and thiols and short reaction times (10 min) with high yields are reported. This protocol introduces a practical and viable green technology of solvent-free and catalyst-free reactions.
- Ghorbani-Vaghei, Ramin,Veisi, Hojat,Amiri, Mostafa,Chegini, Mohammad,Karimi, Mehdi,Dadamahaleh, Somayeh Akbari,Sedrpoushan, Alireza
-
experimental part
p. 39 - 43
(2010/09/03)
-
- Silica sulfuric acid and AI(HSO4)3: As efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions
-
A mixture of ethyl formate and a catalytic amount of silica sulfuric acid or Al(HSO4)3 as suitable formylating systems can formylate various alcohols to their corresponding formate ester derivatives under mild, nearly neutral and heterogeneous conditions at room temperature with good to excellent yields.
- Zolfigol, Mohammad Ali,Chehardoli, Gholamabbas,Dehghanian, Mina,Niknam, Khodabakhsh,Shirini, Farhad,Khoramabadi-Zad, Ahmad
-
experimental part
p. 885 - 889
(2009/12/04)
-
- Efficient acetylation and formylation of alcohols in the presence of Zr(HSO4)4
-
Acetylation and formylation of alcohols with acetic and formic acids have been carried out in the presence of catalytic amounts of Zr(HSO 4)4 under mild and heterogeneous conditions.
- Shirini, Farhad,Zolfigol,Safari
-
p. 154 - 156
(2007/10/03)
-
- Efficient one-step conversion of tetrahydropyranyl ethers into acetates and formates in the presence of potassium dodecatungstocobaltate K 5CoW12O40·3H2O
-
Tetrahydropyranyl ethers derived from primary alcohols were directly and efficiently converted into the corresponding acetates and formates by the action of ethyl acetate, acetic acid, acetic anhydride, and ethyl formate in the presence of a catalytic amount of potassium dodecatungstocobaltate K 5CoW12O40 ? 3H2O. Tetrahydropyranyl ethers derived from secondary alcohols and phenols can also be transformed into the corresponding acetates with the use of acetic anhydride, but K5CoW12O40 ? 3H2O was ineffective for esterification with ethyl acetate, acetic acid, and ethyl formate.
- Rafiee,Tangestaninejad,Habibi,Mohammadpoor-Baltork,Mirkhani
-
p. 393 - 395
(2007/10/03)
-
- Acetylation and formylation of alcohols in the presence of silica sulfuric acid
-
Alcohols are converted to esters in a mild, clean, and efficient reaction with acetic and formic acids in the presence of silica sulfuric acid. All reactions were performed under mild and completely heterogeneous conditions in refluxing n-hexane.
- Shirini, Farhad,Zolfigol, Mohammad Ali,Mohammadi, Kamal
-
p. 1617 - 1621
(2007/10/03)
-
- Reactions of active methylene compounds with benzhydrol during solvolysis in formic acid
-
Formic acid reacts with benzhydrol to give benzhydryl formate, which reacts with active methylene compounds in refluxing formic acid to give either C-alkylation or Ritter reaction products. The product formed is determined by the equilibrium enol content of the active methylene compound. These reaction conditions avoid the use of halogenated reaction solvents, and the pure products are isolated without recourse to chromatography.
- Gullickson, Glen C.,Lewis, David E.
-
p. 385 - 388
(2007/10/03)
-
- Selective formylation of alcohols in the presence of phenols with chloral
-
Primary and secondary alcohols were formylated selectively in the presence of phenols by stirring with chloral in acetone over anhydrous K2CO3 at ambient temperatures in high yields.
- Ram, Ram N,Meher, Nabin Kumar
-
p. 2997 - 3001
(2007/10/03)
-
- Nucleophilic substitution in diphenylmethyl derivatives. I. Formolysis of diarylmethyl derivatives: an α-substituent effect
-
The reactions of formic acid with and without addition of sodium formate with diphenylmethanol (4) and chlorodiphenylmethane (3) were compared to those with hydroxydiphenylacetic (benzilic) acid (12a) and chlorodiphenylacetic acid (14a).Formic acid did not favour any SN1-type reaction on 4, but a strong catalysis by iodide ion was observed.Sodium formate rapidly performed the substitution of the chlorine in 3.A similar outcome was obtained with chloro acid 14a, but the rationalization of the results is different.Chloro acid 14a and its methyl ester 14b were prompt to react, but the equilibria were shiftet to α-formyloxy products 13 only by the addition of HCOONa.HCOOH was unable to perform any reduction on either 3 or 4 or 12a and 14a, a fact which was taken as evidence for concerted substitution mechanism on ion pairs or betaine 15.Mechanistic implications are drawn.
- Strazzolini, Paolo,Giumanini, Angelo G.,Verardo, Giancarlo
-
-