- Facile oxidation of aldehydes to esters using S·SnO 2/SBA-1-H2O2
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A highly efficient, mild, and simple procedure has been described for the oxidation of aldehydes to corresponding esters in alcohols with S·SnO2/SBA-1 as catalyst and H2O2 as the oxidant, and the catalytic systems can be used in the preparation of a broad range of esters. Oxidation of aldehydes to corresponding esters utilizing H 2O2 as the oxidant without any metal catalyst is also reported.
- Qian, Guang,Zhao, Rui,Ji, Dong,Lu, Gaomeng,Qi, Yanxing,Suo, Jishuan
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- PEPTIDOMIMETIC N5-METHYL-N2-(NONANOYL-L-LEUCYL)-L-GLUTAMINATE DERIVATIVES, TRIAZASPIRO[4.14]NONADECANE DERIVATIVES AND SIMILAR COMPOUNDS AS INHIBITORS OF NOROVIRUS AND CORONAVIRUS REPLICATION
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Peptidomimetic N5-methyl-N2-(nonanoyl-L-leucyl)-L-glutaminate derivatives, triazaspiro[4.14]nonadecane derivatives and similar compounds for use in methods of inhibiting the replication of noroviruses and coronaviruses in a biological sample or patient, for use in reducing the amount of noroviruses or coronaviruses in a biological sample or patient, and for use in treating norovirus and coronavirus in a patient, comprising administering to said biological sample or patient a safe and effective amount of a compound represented by formulae I or II, or a pharmaceutically acceptable salt thereof. The present description discloses the synthesis and characterisation of exemplary compounds as well as pharmacological data thereof (e.g. page 99 to page 271; examples 1 to 3; compounds A1 to A104 and Bl to B66; tables A to E).
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Paragraph 00455; 00470
(2021/09/26)
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- Divergent Synthesis of α-Fluorinated Carbonyl and Carboxyl Derivatives by Double Electrophilic Activation of Amides
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A straightforward and divergent entry to α-fluorinated carbonyl and carboxyl derivatives is reported. Upon activation of amides with triflic anhydride and a 2-halo-pyridine and subsequent trapping of the resulting keteniminium ions with nucleophiles followed by a second electrophilic activation with NFSI and final hydrolysis, a range of amides can be transformed to α-fluorinated ketones, esters, and amides under mild conditions. Moreover, this reaction can be performed to yield enantioenriched products with a traceless chiral auxiliary.
- Dubart, Amaury,Evano, Gwilherm
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supporting information
p. 8931 - 8936
(2021/11/17)
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- Design, Synthesis, and Study of the Insecticidal Activity of Novel Steroidal 1,3,4-Oxadiazoles
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A series of novel steroidal derivatives with a substituted 1,3,4-oxadiazole structure was designed and synthesized, and the target compounds were evaluated for their insecticidal activity against five aphid species. Most of the tested compounds exhibited potent insecticidal activity against Eriosoma lanigerum (Hausmann), Myzus persicae, and Aphis citricola. Compounds 20g and 24g displayed the highest activity against E. lanigerum, showing LC50 values of 27.6 and 30.4 μg/mL, respectively. Ultrastructural changes in the midgut cells of E. lanigerum were detected by transmission electron microscopy, indicating that these steroidal oxazole derivatives might exert their insecticidal activity by destroying the mitochondria and nuclear membranes in insect midgut cells. Furthermore, a field trial showed that compound 20g exhibited effects similar to those of the positive controls chlorpyrifos and thiamethoxam against E. lanigerum, reaching a control rate of 89.5% at a dose of 200 μg/mL after 21 days. We also investigated the hydrolysis and metabolism of the target compounds in E. lanigerum by assaying the activities of three insecticide-detoxifying enzymes. Compound 20g at 50 μg/mL exhibited inhibitory action on carboxylesterase similar to the known inhibitor triphenyl phosphate. The above results demonstrate the potential of these steroidal oxazole derivatives to be developed as novel pesticides.
- Bai, Hangyu,Jiang, Weiqi,Li, Qi,Li, Tian,Ma, Shichuang,Shi, Baojun,Wu, Wenjun
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p. 11572 - 11581
(2021/10/12)
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- Hydrofunctionalization of olefins to value-added chemicals: Via photocatalytic coupling
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A green strategy was developed for the synthesis of various value-added chemicals using methanol, acetonitrile, acetic acid, acetone and ethyl acetate as the hydrogen source by coupling them with olefins over heterogeneous photocatalysts. A radical coupling mechanism was proposed for the hydrofunctionalization of olefins with methanol to higher aliphatic alcohols over the Pt/TiO2 catalyst as the model reaction. C-H bond cleavage and C-C bond formation between photogenerated radicals and terminal olefins were accomplished in a single reaction at high efficiency. Our approach is atomically economical with high anti-Markovnikov regioselectivity and promising application potential under mild reaction conditions.
- Fan, Yonghui,Li, Shenggang,Bao, Jingxian,Shi, Lei,Yang, Yanzhang,Yu, Fei,Gao, Peng,Wang, Hui,Zhong, Liangshu,Sun, Yuhan
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supporting information
p. 3450 - 3456
(2018/08/06)
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- Hydroethoxycarbonylation of α-olefins at low pressure of carbon(II) oxide in the presence of the PdCl2(PPh3)2–PPh3–AlCl3 system
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High catalytic activity of the PdCl2(PPh3)2–PPh3–AlCl3 system containing AlCl3 as promotor has been demonstrated in the reaction of hydroethoxycarbonylation of hexene-1 and octene-1 at low pressure of carbon(II) oxide (≤25 atm). The reaction yields linear and branched products. The optimal conditions of the process have been elaborated. The target products yield is 84.6–93.8%.
- Suerbaev, Kh. A.,Kudaibergenov, N. Zh.,Vavasori
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p. 707 - 712
(2017/05/29)
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- The scope and mechanism of palladium-catalysed Markovnikov alkoxycarbonylation of alkenes
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Hydroesterification reactions represent a fundamental type of carbonylation reaction and constitute one of the most important industrial applications of homogeneous catalysis. Over the past 70 years, numerous catalyst systems have been developed that allow for highly linear-selective (anti-Markovnikov) reactions and are used in industry to produce linear carboxylates starting from olefins. In contrast, a general catalyst system for Markovnikov-selective alkoxycarbonylation of aliphatic olefins remains unknown. In this paper, we show that a specific palladium catalyst system consisting of PdX2/N-phenylpyrrole phosphine (X, halide) catalyses the alkoxycarbonylation of various alkenes to give the branched esters in high selectivity (branched selectivity up to 91%). The observed (and unexpected) selectivity has been rationalized by density functional theory computation that includes a dispersion correction.
- Li, Haoquan,Dong, Kaiwu,Jiao, Haijun,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
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p. 1159 - 1166
(2016/11/28)
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- PROCESS FOR PREPARING ESTERS FROM FORMATES AND OLEFINICALLY UNSATURATED COMPOUNDS
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The invention provides a process for preparing esters from formates and olefinically unsaturated compounds with catalysts based on palladium compounds. In addition, the invention discloses a polyphasic reaction mixture and nonyl methyl ester mixtures prepared by the process according to the invention.
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Paragraph 0060; 0063
(2014/10/29)
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- Palladium complexes with N-heterocyclic carbene ligands as catalysts for the alkoxycarbonylation of olefins
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Palladium catalysts, generated from Pd(OAc)2 and 2 equiv of N,N-dialkylbenzimidazolium iodide, are effective for the alkoxycarbonylation of olefins in high yields (>90%). Alkoxycarbonylation of 1-hexene in dimethylacetamide is achieved within 24 h at 110 C using 1 mol % catalyst, 1000 psi CO, and ethanol. Reactions can be prepared in air, without the need of an acid additive to produce ethyl 2-methylhexanoate and ethyl heptanoate in approximately a 2:1 ratio.
- Roberts, Gina M.,Pierce, Philip J.,Woo, L. Keith
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p. 2033 - 2036
(2013/05/21)
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- A unique palladium catalyst for efficient and selective alkoxycarbonylation of olefins with formates
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Forget about CO! Carbonylations are among the most important homogeneously catalyzed reactions in the chemical industry, but typically require carbon monoxide. Instead, straightforward and efficient alkoxycarbonylations of olefins can proceed with alkyl formates in the presence of a specific palladium catalyst. Aromatic, terminal aliphatic, and internal olefins are carbonylated to give industrially important linear esters at low catalyst loadings. Copyright
- Fleischer, Ivana,Jennerjahn, Reiko,Cozzula, Daniela,Jackstell, Ralf,Franke, Robert,Beller, Matthias
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p. 417 - 420
(2013/04/24)
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- Pd/light-accelerated atom-transfer carbonylation of alkyl iodides: Applications in multicomponent coupling processes leading to functionalized carboxylic acid derivatives
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The atom-transfer carbonylation reaction of various alkyl iodides thereby leading to carboxylic acid esters was effectively accelerated by the addition of transition-metal catalysts under photoirradiation conditions. By using a combined Pd/hv reaction system, vicinal C-functionalization of alkenes was attained in which α-substituted iodoalkanes, alkenes, carbon monoxide, and alcohols were coupled to give functionalized esters. When alkenyl alcohols were used as acceptor alkenes, three-component coupling reactions, which were accompanied by intramolecular esterification, proceeded to give lactones. Pd-dimer complex [Pd2(CNMe)6][PF6]2, which is known to undergo homolysis under photoirradiation conditions, worked quite well as a catalyst in these three- or four-component coupling reactions. In this metal/radical hybrid system, both Pd radicals and acyl radicals are key players and a stereochemical study confirmed the carbonylation step proceeded through a radical carbonylation mechanism. Light, camera, ATCion: Atom-transfer carbonylation of alkyl iodides to afford carboxylic acid esters was accelerated by the addition of transition-metal catalysts under photoirradiation. The carbonylation step proceeded through a radical mechanism. Copyright
- Fusano, Akira,Sumino, Shuhei,Nishitani, Satoshi,Inouye, Takaya,Morimoto, Keisuke,Fukuyama, Takahide,Ryu, Ilhyong
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supporting information; experimental part
p. 9415 - 9422
(2012/08/27)
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- Synthesis and insecticidal activities of 1,3,5-trisubstituted-1,3,5- hexahydrotriazine-2-N-nitroimines
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A new series of 1,3,5-trisubstituted-1,3,5-hexahydrotriazine-2-N- nitroimines (3a-3j) were designed and synthesized as novel neonicotinoid analogues, and their structures were characterized by 1H NMR, IR, elemental analysis and MS. The preliminary bioassay tests showed that most of the target compounds had good insecticidal activities against Nilaparvata lugens as well as Aphis medicaginis at 500 mg/L, while compound 3i had 100% mortality against Nilaparvata lugens at 20 mg/L.
- Xue, Sijia,Ma, Xubo,Bu, Hongfei,Liu, Li,Xu, Xiao
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p. 2153 - 2156
(2012/03/26)
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- A clean, palladium-catalyzed oxidative esterification of aldehydes using benzyl chloride
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A highly efficient, mild, simple and clean procedure is presented for the one-pot oxidation of aromatic and aliphatic aldehydes to their corresponding ethyl esters using benzyl chloride as the oxidant under palladium-catalyzed conditions. The reaction is complete in just 30 min under microwave irradiation and inert conditions are not required to obtain good to excellent yields (65-93%) of isolated products.
- Heropoulos, Georgios A.,Villalonga-Barber, Carolina
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experimental part
p. 5319 - 5322
(2011/10/31)
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- Tandem one-pot conversion of aldehydes into ethyl esters
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A facile one-pot synthesis of ethyl esters from aldehydes has been developed. This tandem process involves the formation of a nitrile intermediate obtained from the reaction of an aldehyde with hydroxylamine hydrochloride in dimethylsulfoxide (DMSO) at 100°C and the subsequent reaction of the nitrile with ethanol and sulfuric acid at 130°C. The resulting ethyl ester products were produced in good yields (65-90%) and high purity (>95%).
- Siler, Patrick J.,Chill, Samuel T.,Mebane, Robert C.
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body text
p. 1247 - 1250
(2011/05/02)
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- Fragmentation of chloroperoxides: Hypochlorite-mediated dehydration of hydroperoxyacetals to esters
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Hypochlorites efficiently dehydrate hydroperoxyacetals to furnish the corresponding esters. The reaction, which can be accomplished with stoichometric Ca(OCl)2 or with catalytic amounts of t-BuOCl, appears to involve formation and heterolytic fragmentation of secondary chloroperoxides, species not previously described in solution chemistry.
- Fisher, Thomas J.,Dussault, Patrick H.
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experimental part
p. 5615 - 5617
(2010/10/21)
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- A new versatile synthesis of esters from Grignard reagents and chloroformates
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Cross-coupling reactions of chloroformates with organocopper reagents, derived from Grignard reagents, cuprous bromide and lithium bromide, provide a rapid and straightforward method for the synthesis of esters. Georg Thieme Verlag Stuttgart.
- Bottalico, Daniela,Fiandanese, Vito,Marchese, Giuseppe,Punzi, Angela
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p. 974 - 976
(2008/02/02)
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- Selective esterification of aliphatic carboxylic acids in the presence of aromatic carboxylic acids over monoammonium salt of 12-tungstophosphoric acid
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Monoammonium salt of 12-tungstophosphoric acid [(NH4)H 2PW12O40] was found to be a practical and useful heterogeneous catalyst for an efficient and selective esterification of aliphatic carboxylic acids with alcohols in the presence of aromatic carboxylic acids. The heteropoly acid-based heterogeneous catalyst has the advantages of a simple workup procedure, water insolubility, and good activity. Copyright Taylor & Francis LLC.
- Giri,Prabhavathi Devi,Gangadhar,Narasimha Rao,Lingaiah,Sai Prasad,Prasad
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- Facile synthesis of highly congested 1,2-diphosphinobenzenes from bis(phosphine)boronium salts
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(Chemical Equation Presented) Bis(phosphine)boronium salts 3a-c were designed and prepared as key building blocks for the synthesis of highly congested diphosphinobenzenes. The preparation of sterically hindered ortho-phenylene-bridged diphosphines 1a-c was achieved by the reaction of the bis(phosphine)boronium salts 3a-c with difluorobenzenechromium complex 2 and subsequent removal of the BH2 group. The steric nature of diphosphine 1a was revealed in single-crystal X-ray analysis of its Rh complex.
- Yamamoto, Yoshikazu,Koizumi, Toru,Katagiri, Kosuke,Furuya, Yui,Danjo, Hiroshi,Imamoto, Tsuneo,Yamaguchi, Kentaro
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p. 6103 - 6106
(2007/10/03)
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- Effective acceleration of atom transfer carbonylation of alkyl iodides by metal complexes. Application to the synthesis of the hinokinin precursor and dihydrocapsaicin
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Atom transfer carbonylation (ATC) of alkyl iodides leading to carboxylic acid esters is effectively accelerated by Pd(PPh3)4 and Mn2(CO)10 under photoirradiation conditions. In the presence of amines, Pd(0) complexes affected double carbonylations leading to α-keto amides, whereas Mn2(CO)10 accelerated only a single carbonylation reaction leading to the corresponding amides. The Pd(0)-accelerated ATC system was successfully applied to the synthesis of hinokinin and dihydrocapsaicin.
- Fukuyama, Takahide,Nishitani, Satoshi,Inouye, Takaya,Morimoto, Keisuke,Ryu, Ilhyong
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p. 1383 - 1386
(2007/10/03)
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- Deuteration of α,β-acetylenic esters, amides, or carboxylic acids without using deuterium gas: Synthesis of 2,2,3,3-tetradeuterioesters, amides, or acids
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An easy, simple, rapid, and nonhazardous deuteration of the C-C triple bond of α,β-acetylenic esters, amides, or acids by means of samarium diiodide in the presence of D2O, provides an efficient method for synthesizing 2,2,3,3-tetradeuterioesters, amides, or carboxylic acids, respectively. When H2O is used instead of D2O, saturated carboxylic esters, amides, or acids were isolated. A mechanism to explain these reduction reactions has been proposed.
- Concellón, José M.,Rodríguez-Solla, Humberto,Concellón, Carmen
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p. 2129 - 2131
(2007/10/03)
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- Nickel-catalyzed cross-coupling reaction of alkyl halides with organozinc and grignard reagents with 1,3,8,10-tetraenes as additives
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Essential additives: The addition of bis(1,3-butadienyl) compounds (tetraenes) was essential in the efficient Nicatalyzed cross-coupling of organozinc reagents with alkyl bromides and a tosylate (see scheme, X = C(CO2Me)2 or NCH2Ph). The efficiency of the Ni-catalyzed cross-coupling of an alkyl fluoride with a Grignard reagent was also improved by using these tetraenes.
- Terao, Jun,Todo, Hirohisa,Watanabe, Hideyuki,Ikumi, Aki,Kambe, Nobuaki
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p. 6180 - 6182
(2007/10/03)
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- Synthesis of 1-Nonanoyl/octadecanoyl-4-substituted Thiosemicarbazides and substituted 1,2,4-Trizoles as biological active compounds
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4-Alkyl/aryl-5-nonanoyl/octadecanoyl-2,4-dihydro-3H-1,2, 4-triazoline-3-thiones were synthesized as potential antimicrobial agents. The course of synthesis included the reaction of nonanoyl/octadecanoyl hydrazines with selected alkyl/aryl isothiocyanates. The prepared thiosemicarbazides gave by cyclization the required 1,2,4-triazoles. A number of synthesized compounds were subjected to in vitro testing against two gram-positive, two gram-negative bacteria and two fungi.
- Colanceska-Ragenovic, Katica,Dimova, Vesna,Kakurinov, Vlado,Gabor, Dora Molnar
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p. 905 - 908
(2007/10/03)
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- Nickel-catalyzed cross-coupling between functionalized primary or secondary alkylzinc halides and primary alkyl halides
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In the presence of Bu4NI (3 equiv) and 4-fluorostyrene (20 mol %), unreactive primary and secondary alkylzinc iodides undergo nickel-catalyzed cross-couplings with various primary alkyl iodides or bromides. More reactive secondary dialkylzincs and the mixed zinc organometallics RZnTMSM undergo the cross-coupling reaction in the absence of Bu4NI. The bicyclic secondary diorganozinc 6 prepared via boron-zinc exchange reacts with high retention of configuration. Free NH-groups are tolerated in the cross-coupling allowing the synthesis of aminated products.
- Jensen, Anne Eeg,Knochel, Paul
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- Selective reduction of α,β-unsaturated esters with NaBH4-BiCl3 system
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Sodium borohydride-bismuth chloride system was applied for the selective reduction of carbon-carbon double bond of α,β-unsaturated esters with high selectivity.
- Ren,Pan,Dong,Wu
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p. 3395 - 3399
(2007/10/03)
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- Carbonylation of alkyl sulfonates catalyzed by cobalt complexes
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Alkyl sulfonates (R1-OSO2R2) react with carbon monoxide and alcohol (R3-OH) in the presence of catalytic amounts of Co complex and Nal to afford the corresponding esters (R1-COOR3) in moderate to good yields.
- Urata, Hisao,Goto, Daisuke,Fuchikami, Takamasa
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p. 3091 - 3094
(2007/10/02)
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- TRANSITION METAL COMPLEX CATALYZED CARBONYLATION OF ORGANIC HALIDES IN THE PRESENCE OF MOLECULAR SIEVES INSTEAD OF BASE
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In the presence of molecular sieves under base free conditions organic halides are successfully carbonylated under carbon monoxide pressure with water or alcohols catalyzed by Co or Pd complex to generate the corresponding carboxylic acids or esters, respectively, in good yields.
- Urata, Hisao,Hu, Nan-Xing,Maekawa, Hisayuki,Fuchikami, Takamasa
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p. 4733 - 4736
(2007/10/02)
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- Triazene Drug Metabolites. Part 9. Base Catalysed Deacylation of 3-Acyl-3-alkyl-1-aryltriazenes in Ethanol.
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3-Acyl-3-alkyl-1-aryltriazenes undergo a base-catalysed deacylation reaction to liberate the corresponding cytotoxic 3-alkyl-1-aryltriazene.Reaction are first-order in both and .Second-order rate constants, k2, depend on the structure of both the substrate and the base.The values of k2 for the deformylation of 1-aryl-3-formyl-3-methyltriazenes by piperidine follow the Hammett relationship giving ρ +2.9; a similar correlation, ρ +1.6, is observed for the morpholine catalysed deacylation of 1-aryl-3-methyl-3-trifluoroacetyltriazenes.For 1-(4-cyanophenyl)-3-methyl-3-trifluoroacetyltriazene, a correlation between the aqueous pKa of the base and k2 is obtained, giving a Broensted β value of 0.36.The solvent deuterium isotope effect, k2EtOH/k2EtOD, for the piperidine-catalysed deacylation of 1-(3-pyridyl)-3-formyl-3-methyltriazene is 2.2, and 2,2,6,6-tetramethylpiperidine is some 2.4 times more effective than piperidine at catalysing the deformylation of this compound.Rate constants for the deacylation of 3-alkyltriazenes diminish in the order Me > Pr > Et.Rate constants also vary with the nature of the acyl group: thus CF3CO > HCO > MeCO > C8H17CO.The data are interpreted in terms of a mechanism that involves a rate-determining, general-base-catalysed attack of a solvent ethanol molecule at the carbonyl carbon atom of the group, followed by rapid collapse of the tetrahedral intermediate to form the monoalkyltriazene.
- Iley, Jim,Ruecroft, Graham,Carvalho, Emilia,Rosa, Eduarda
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p. 1264 - 1273
(2007/10/02)
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- Process for the preparation of D(+)-biotin
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The stereospecific preparation of D(+)-biotin is improved by a synthetic route involving the conversion of 3,4-isopropylidene-D-arabinose in which the OH group in the 2-position is not protected, into an ester of 6,9-dihydroxy-7,8-isopropylidenedioxynona-2,4-dienoic acid, the latter then being catalytically hydrogenated and subsequently converted into D(+)-biotin in a manner known per se.
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- HYDROFORMYLATION AND CARBOXYLATION OF OLEFINS IN PRESENCE OF STANNYLENE COMPLEXES OF METAL CARBONYLS
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Stannous chloride is an activator for chromium molybdenum, and tungsten hexacarbonyls as catalysts in hydroformylation and carboxylation processes.It is considered that the catalysts of the processes are stannylene complexes formed in situ from chromium, molybdenun, and tungsten hexacarbonyls and stannous chloride.
- Magomedov, G. K.-I.,Morozova, L. V.
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p. 1947 - 1950
(2007/10/02)
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- PHOTOCHEMICAL ACTIVATION OF THE CARBOXYL GROUP VIA N-ACYL-2-THIONOTHIAZOLIDINES
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Photolysis of N-acyl derivatives of 2-thionothiazolidine in the presence of ethanol affords ethyl esters; a mechanism involving γ-hydrogen abstraction by sulfur is postulated.
- Burton, Lester P.J.,White, James D.
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p. 3147 - 3150
(2007/10/02)
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- Processes for regenerating dispersions of ligand stabilized, palladium and platinum (II) halide-complexes used in carbonylation and hydroformylation catalysts
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This invention concerns using mineral acid treatment for the regeneration of carbonylation and hydroformylation catalysts consisting of dispersions of ligand-stabilized palladium(II) and platinum(II) halide complexes in quaternary ammonium, phosphonium and arsonium salts of trihalostannate(II) and trihalogermanate(II).
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- Carbonylation of olefins and acetylenes
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Olefins and acetylenes are carbonylated to a carboxylic acid or ester using a homogenous catalyst system comprising palladium together with iron or a metal of Groups IVA, VA or IIIB, the catalyst being either a polynuclear complex incorporating both metals, or a mixture of a soluble palladium salt and metal halide. Starting with cyclic di-olefins, such as cyclo-octadiene, the product cycloalkenyl carboxylic acid or ester may be cleaved to give acyclic dicarboxylic acids, such as azelaic acid.
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