- Photo-on-Demand Synthesis of Vilsmeier Reagents with Chloroform and Their Applications to One-Pot Organic Syntheses
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The Vilsmeier reagent (VR), first reported a century ago, is a versatile reagent in a variety of organic reactions. It is used extensively in formylation reactions. However, the synthesis of VR generally requires highly toxic and corrosive reagents such as POCl3, SOCl2, or COCl2. In this study, we found that VR is readily obtained from a CHCl3 solution containing N,N-dimethylformamide or N,N-dimethylacetamide upon photo-irradiation under O2 bubbling. The corresponding Vilsmeier reagents were obtained in high yields with the generation of gaseous HCl and CO2 as byproducts to allow their isolations as crystalline solid products amenable to analysis by X-ray crystallography. With the advantage of using CHCl3, which bifunctionally serves as a reactant and a solvent, this photo-on-demand VR synthesis is available for one-pot syntheses of aldehydes, acid chlorides, formates, ketones, esters, and amides.
- Liang, Fengying,Eda, Kazuo,Okazoe, Takashi,Wada, Akihiro,Mori, Nobuaki,Konishi, Katsuhiko,Tsuda, Akihiko
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p. 6504 - 6517
(2021/05/06)
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- Formyloxyacetoxyphenylmethane and 1,1-diacylals as versatile O-formylating and O-acylating reagents for alcohols
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Formyloxyacetoxyphenylmethane, symmetric 1,1-diacylals and mixed 1-pivaloxy-1-acyloxy-1-phenylmethanes have been used as moisture stable O-formylating and O-acylating reagents for primary and secondary alcohols, allylic alcohols and phenols under solvent/catalyst free conditions to afford their corresponding esters in good yield.
- Chapman, Robert S.L.,Francis, Molly,Lawrence, Ruth,Tibbetts, Joshua D.,Bull, Steven D.
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p. 6442 - 6452
(2018/10/02)
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- N-Heterocyclic Carbene Catalyzed Transformylation
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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.
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p. 3505 - 3510
(2017/07/27)
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- Acidic ionic liquid immobilized on nanoporous Na+-montmorillonite as an efficient and reusable catalyst for the formylation of amines and alcohols
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In this work, nanoporous sodium montmorillonite clay (Na+-MMT) was used as a support for the immobilization of 1-methyl-3-(trimethoxysilylpropyl)-imidazolium hydrogen sulfate. The Na+-MMT chemical modification ([Na+-MMT-[pmim]HSO4) was confirmed by a variety of techniques including Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), thermogravimetric analysis (TGA), scanning electron microscopy and potentiometric titration. The catalytic performance of this immobilized acidic ionic liquid was probed for the N-formylation of a variety of amines using formic acid under solvent-free conditions. This reagent is also useful for the formylation of benzylic alcohols. The procedure gave the products in excellent yields in very short reaction times. Also, this catalyst can be reused ten times without loss of its catalytic activity.
- Shirini, Farhad,Mazloumi, Masoumeh,Seddighi, Mohadeseh
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p. 1759 - 1776
(2016/03/16)
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- Formylation of amines and alcohols using aminopropylated mesoporous SBA-15 silica (APMS) as an efficient and recyclable catalyst
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Aminopropylated mesoporous SBA-15 silica (APMS) is introduced as a new, recyclable and efficient catalyst for the formylation of a variety of amines and alcohols by using readily available formic acid under solvent-free conditions.
- Malakooti, Reihaneh,Sobhani, Sara,Razavi, Nasrin,Shafiei, Soheila,Mokhtari, Rezvan
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experimental part
p. 1979 - 1990
(2012/04/17)
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- Dual behavior of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions
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The dual behavior phenomenon of alcohols in iodine-catalyzed esterification under solvent-free reaction conditions (SFRCs) is described; the governing factor is the stability of the carbonium ion generated from the alcohol; high concentration reaction conditions (HCRCs) or dilute solutions are much less suitable. In the case of benzylic alcohols, loss of optical activity was noted, whereas alkyl alcohols furnished a product with retention of stereochemistry.
- Jereb, Marjan,Vra?i?, Dejan,Zupan, Marko
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body text
p. 2347 - 2352
(2009/09/06)
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- Silica sulfuric acid and AI(HSO4)3: As efficient catalysts for the formylation of alcohols by using ethyl formate under heterogeneous conditions
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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
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experimental part
p. 885 - 889
(2009/12/04)
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- Silica triflate as an efficient reagent for the chemoselective formylation of alcohols
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Silica triflate, as a new and stable silica-based reagent, is prepared by a reaction of silica gel with trifluoromethane sulfonyl chloride at room temperature. This reagent can be used for the efficient and selective formylation of alcohols in the presence of phenols in a relatively short reaction time and high yields under heterogeneous reaction conditions.
- Shirini, Farhad,Marjani, Katayoun,Nahzomi, Hossein Taherpour,Zolfigol, Mohammad Ali
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p. 1245 - 1251
(2008/02/05)
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- Efficient acetylation and formylation of alcohols in the presence of Zr(HSO4)4
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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
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p. 154 - 156
(2007/10/03)
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- Efficient one-step conversion of tetrahydropyranyl ethers into acetates and formates in the presence of potassium dodecatungstocobaltate K 5CoW12O40·3H2O
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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
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p. 393 - 395
(2007/10/03)
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- Silphos [PCl3-n(SiO2)n]: A heterogeneous phosphine reagent for formylation and acetylation of alcohols and amines with ethyl formate and acetate
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Alcohols and amines are formylated and acetylated in the presence of Silphos [PCl3-n(SiO2)n] in ethyl formate and ethyl acetate in high to excellent yields. This procedure provides a method to separate the product by a simple filtration.
- Iranpoor, Nasser,Firouzabadi, Habib,Jamalian, Arezu
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p. 7963 - 7966
(2007/10/03)
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- Vilsmeier-Haack Reagents. Novel Electrophiles for the One-Step Formylation of O-Silylated Ethers to O-Formates
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Various O-silylated substrates were effectively converted in one-step to their corresponding O-formates using electrophilic racemic and homochiral Vilsmeier-Haack reagents. Reactivity trends of these transformations were examined that, specifically, empha
- Lellouche, Jean-Paul,Kotlyar, Vadim
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p. 564 - 571
(2007/10/03)
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- Cerium polyoxometalate as a reusable catalyst for acetylation and formylation of alcohols
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Efficient esterification of primary and sterically-hindered secondary or tertiary alcohols with acetic anhydride was achieved in the presence of ammonium decatungestocerate(IV) icosahydrate, (NH4)8[CeW 10O36]·OH2O, as catalyst in high yields. Primary and secondary alcohols were also converted to their corresponding acetates and formates with acetic acid and ethyl formate in the presence of this catalyst. Easy work-up, non-toxicity, reusability, and stability of the catalyst are noteworthy advantages of this method. Springer-Verlag 2004.
- Mirkhani, Valiollah,Tangestaninejad, Shahram,Moghadam, Majid,Yadollahi, Bahram,Alipanah, Ladan
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p. 1257 - 1263
(2007/10/03)
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- Bi(III) salts as new catalysts for the selective conversion of trimethylsilyl and tetrahydropyranyl ethers to their corresponding acetates and formates
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Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3 were found to be efficient catalysts for the transformation of trimethylsilyl (TMS) and tetrahydropyranyl (THP) ethers to their corresponding acetates and formates with acetic acid and ethyl formate. Selective acetylation and formylation of TMS and THP ethers of alcohols in the presence of phenolic TMS and THP ethers make this method a useful and practical procedure in organic synthesis.
- Mohammadpoor-Baltork,Khosropour
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p. 2433 - 2439
(2007/10/03)
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- 2,2,2-trifluoroethyl formate: a versatile and selective reagent for the formylation of alcohols, amines, and N-hydroxylamines.
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[reaction: see text] Treatment of a variety of alcohols, amines, and N-hydroxylamines with 2,2,2-trifluoroethyl formate gave the corresponding formylated adducts in high yields.
- Hill, David R,Hsiao, Chi-Nung,Kurukulasuriya, Ravi,Wittenberger, Steven J
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p. 111 - 113
(2007/10/03)
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- Reaction of C2-symmetrical dialkoxysilanes R1O-Si(R2)2-OR1 with the two Vilsmeier-Haack complexes POCl3·DMF and (CF3SO2)2O·DMF: An efficient one-step conversion to the
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The two electrophilic Vilsmeier-Haack complexes POCl3·DMF 1 and (CF3SO2)2O·DMF 2 react with C2-symmetrical dialkoxysilanes R1O-Si(R2)2-OR1 (R1=(-)-menthyl o
- Cohen,Kotlyar,Koeller,Lellouche
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p. 1543 - 1546
(2007/10/03)
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- A convenient and chemoselective acetylation and formylation of alcohols and phenols using acetic acid and ethyl formate in the presence of Bi(III) salts
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A variety of alcohols are acetylated and formylated efficiently with acetic acid and ethyl formate in the presence of catalytic amounts of Bi(III) salts such as BiCl3, Bi(TFA)3 and Bi(OTf)3. BiCl3 and Bi(OTf)3 are also effective catalysts for acetylation of phenols. All of these catalysts are ineffective in formylation of phenols. Selective acetylation and formylation of alcohols in the presence of phenols is an additional advantage of this procedure.
- Mohammadpoor-Baltork,Khosropour,Aliyan
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p. 280 - 282
(2007/10/03)
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- Novel catalytic acetylation and formylation of alcohols with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O)
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Acetylation and formylation reactions of alcohols with ethyl acetate, acetic acid and ethyl formate were catalyzed with potassium dodecatungstocobaltate trihydrate (K5CoW12O40·3H2O) in a mild, efficient and convenient method with high to excellent yields.
- Habibi, Mohammad H,Tangestaninejad, Shahram,Mirkhani, Valiollah,Yadollahi, Bahram
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p. 8333 - 8337
(2007/10/03)
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- Conversion of trimethylsilyl ethers to acetyl or formyl esters with TiCl4
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A simple method is described for the efficient conversion of trimethylsilyl ethers to their corresponding acetyl and formyl esters in refluxing ethyl acetate or ethyl formate in the presence of TiCl4.
- Iranpoor, Nasser,Zeynizadeh, Behzad
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p. 2123 - 2128
(2007/10/03)
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- Preparation of formate esters from O-TBDMS/O-TES protected alcohols. A one-step conversion using the Vilsmeier-Haack complex POCl3/DMF
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O-tert-Butyldimethylsilylated (O-TBDMS) or O-triethylsilylated (O-TES) alcohols were converted in one step to their corresponding formates under Vilsmeier-Haack conditions (POCl3/DMF). The scope and limitations of this novel reaction for interconverting alcohol protecting groups are described.
- Koeller, Sylvain,Lellouche, Jean-Paul
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p. 7043 - 7046
(2007/10/03)
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- Catalytic esterification of alcohols, carboxylic acids and transesterification reactions with cerium(IV) triflate
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Esterification reactions of alcohols with acetic, chloroacetic, trifluoroacetic, propionic, stearic, and benzoic acids were catalyzed with Ce(OTf)4 in a solvent or under solvent-free conditions with high yields. The formylation and acetylation of primary and secondary alcohols were also easily achieved in ethyl formate and ethyl acetate. A high retention of the configuration was observed in the acetylation and formylation of (-)-menthol.
- Iranpoor, Nasser,Shekarriz, Marzieh
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p. 455 - 458
(2007/10/03)
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- Acetylation and formylation of alcohols with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl formate
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Alcohols were acetylated or formylated with triphenylphosphine and carbon tetrabromide in ethyl acetate or ethyl (or methyl) formate at room temperature. THP or TBDMS ether of primary alcohol got converted into formate or acetate under the experimental conditions employed in one pot operation.
- Hagiwara, Hisahiro,Morohashi, Kimie,Sakai, Hitoshi,Suzuki, Toshio,Ando, Masayoshi
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p. 5845 - 5852
(2007/10/03)
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- Selective acetylation of primary alcohols: Acetyl and formyl transfer reactions with copper(II) salts
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The efficient esterification of primary and secondary alcohols in acetic acid was achieved in the presence of Cu(NO3)2. 3H20 in high yields. Selective acetylation of primary in the presence of secondary hydroxyl groups in excellent yields were performed in EtOAc. Formylation of primary and secondary alcohols was also achieved easily in ethyl formate. High retention of configuration was observed in the acetylafion and formylation of (-) menthol in the presence of Cu(NO3)2. 3H20 and Cu(OAC)2. H2O.
- Iranpoor,Firouzabadi,Zolfigol
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p. 1923 - 1934
(2007/10/03)
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- N-Formylbenzotriazole: A stable and convenient N- and O-formylating agent
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N-Formylbenzotriazole, prepared by the reaction of benzotriazole and formic acid in the presence of dicyclohexylcarbodiimide, is demonstrated to be a superior N- and O-formylating agent.
- Katritzky,Chang,Yang
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p. 503 - 505
(2007/10/02)
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- Enol Formates: Ruthenium Catalysed Formation and Formylating Reagents
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The one-step synthesis of the enol formates, isopropenyl, hex-1-en-2-yl, and α-methylenebenzyl formates, directly from terminal alkynes and formic acid with arene-ruthenium(II) catalysts is reported.They have been shown to be effective formylating reagents, under mild and neutral conditions, to produce formamides from primary and secondary amines, formylamino esters, and in the presence of a catalytic amount of imidazole, formates from alcohols or phenols.
- Neveux, Muriel,Bruneau, Christian,Dixneuf, Pierre H.
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p. 1197 - 1199
(2007/10/02)
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- Process for inverting the configuration of secondary alcohols
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Process for inverting the configuration of secondary alcohols in which the hydroxyl group is attached to an asymmetric carbon atom, in accordance with which the secondary alcohols are esterified, with inversion of their configuration, by conversion into isourea ethers and reaction of these isourea ethers with carboxylic acids, and the esters are then saponified with retention of the configuration of the secondary alcohols.
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- POLYMER-SUPPORTED PHOSPHINE-HALOGEN COMPLEXES - 4. IMPROVED FORMYLATION OF ALCOHOLS WITH DIMETHYLFORMAMIDE
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A new, very convenient procedure for smooth conversion of primary and secondary alcohols to their corresponding formic acid esters is described.This is based on the use of modified Vilsmeier-Haak adducts, obtained from N,N-dimethylformamide and polymer-supported triarylphosphine-halogen complexes.
- Caputo, Romualdo,Ferreri, Carla,Palumbo, Giovanni
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p. 1629 - 1636
(2007/10/02)
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