- Method for preparing amino alcohol derivative
-
The invention provides a method for preparing an amino alcohol derivative. The method is characterized in that substitution reaction is carried out on ester groups of dihydric alcohol carboxylic esteror polyhydric alcohol carboxylic ester to obtain the amino alcohol derivative, wherein the amidogen is derived into sulfonamido, and at least one carboxylic ester group remains. The method for preparing the amino alcohol derivative has the advantages that the raw materials are cheap and obtained easily, the use quantity of catalysts is low, the reaction condition is simple, and the selectivity ofproducts is high.
- -
-
Paragraph 0093; 0094; 0095
(2018/11/22)
-
- Vicinal Difunctionalization of Alkenes under Iodine(III) Catalysis involving Lewis Base Adducts
-
The influence of a 2-pyridinyl substituent on the catalytic performance of aryl iodides as catalyst in iodine(III) chemistry was explored. An efficient Lewis base adduct between the pyridine nitrogen and the electrophilic iodine(III) center was identified and confirmed by X-ray analysis. This arrangement was shown to generate a kinetically competent superior catalyst structure for the catalytic dioxygenation of alkenes. It introduces the concept of Lewis base adduct formation as a kinetic factor in iodine(I/III) catalysis. (Figure presented.).
- Aertker, Kristina,Rama, Raquel J.,Opalach, Julita,Mu?iz, Kilian
-
supporting information
p. 1290 - 1294
(2017/04/18)
-
- Mechanistically Driven Development of an Iron Catalyst for Selective Syn-Dihydroxylation of Alkenes with Aqueous Hydrogen Peroxide
-
Product release is the rate-determining step in the arene syn-dihydroxylation reaction taking place at Rieske oxygenase enzymes and is regarded as a difficult problem to be resolved in the design of iron catalysts for olefin syn-dihydroxylation with potential utility in organic synthesis. Toward this end, in this work a novel catalyst bearing a sterically encumbered tetradentate ligand based in the tpa (tpa = tris(2-methylpyridyl)amine) scaffold, [FeII(CF3SO3)2(5-tips3tpa)], 1 has been designed. The steric demand of the ligand was envisioned as a key element to support a high catalytic activity by isolating the metal center, preventing bimolecular decomposition paths and facilitating product release. In synergistic combination with a Lewis acid that helps sequestering the product, 1 provides good to excellent yields of diol products (up to 97% isolated yield), in short reaction times under mild experimental conditions using a slight excess (1.5 equiv) of aqueous hydrogen peroxide, from the oxidation of a broad range of olefins. Predictable site selective syn-dihydroxylation of diolefins is shown. The encumbered nature of the ligand also provides a unique tool that has been used in combination with isotopic analysis to define the nature of the active species and the mechanism of activation of H2O2. Furthermore, 1 is shown to be a competent synthetic tool for preparing O-labeled diols using water as oxygen source.
- Borrell, Margarida,Costas, Miquel
-
supporting information
p. 12821 - 12829
(2017/09/25)
-
- Direct oxidative lactonization of alkenoic acids mediated solely by NaIO4: Beyond a simple oxidant
-
Triflic acid-catalyzed direct oxidative lactonization of alkenoic acids mediated solely by NaIO4 without halogen salts is described. Sodium periodate works not only as an oxidant, but also as an active reagent and directly mediates the lactonization. A new cheap, green, and practical oxidative lactonization approach has been developed using NaIO4 as the sole reagent.
- Kang, Yan-Biao,Chen, Xian-Min,Yao, Chuan-Zhi,Ning, Xiao-Shan
-
supporting information
p. 6193 - 6196
(2016/05/19)
-
- Aerobic Acetoxyhydroxylation of Alkenes Co-catalyzed by Organic Nitrite and Palladium
-
An aerobic acetoxyhydroxylation of alkenes cooperatively catalyzed by organic nitrite and palladium at room temperature using clean and cheap air as the sole oxidant has been developed. Various vicinal diols, diacetoxyalkanes, and dihalogenoalkanes have been synthesized. The gram-scale synthesis has also been approached. Vicinal difluorination and dichlorolation products have also been achieved via this reaction.
- Chen, Xian-Min,Ning, Xiao-Shan,Kang, Yan-Biao
-
supporting information
p. 5368 - 5371
(2016/11/02)
-
- Iron-Catalyzed Dioxygenation of Alkenes and Terminal Alkynes by using (Diacetoxyiodo)benzene as Oxidant
-
An iron-catalyzed syn-diacetoxylation of alkenes and 1,2-oxyacetoxylation of terminal alkynes has been developed using (diacetoxyiodo)benzene as oxidant. A broad range of internal and terminal alkenes, including electron-rich as well as electron-deficient alkenes, gave the desired products in good to excellent yields with high diastereoselectivity (up to >99:1 dr). In addition the high catalytic activity of iron catalysis for the 1,2-oxyacetoxylation of terminal alkynes is also reported. The roles of catalyst, oxidant and other reaction parameters were evaluated for activation of the unsaturated bond.
- Srinivas,Rawat, Vikas S.,Sreedhar, Bojja
-
supporting information
p. 3587 - 3596
(2016/01/25)
-
- Metal-free, organocatalytic syn diacetoxylation of alkenes
-
A novel method for the organocatalytic syn diacetoxylation of alkenes has been developed using aryl iodides as efficient catalysts. A broad range of substrates, including electron-rich as well as electron-deficient alkenes, are smoothly transformed by the new procedure, furnishing the desired products in good to excellent yields with high diastereoselectivity (up to >19:1 dr).
- Zhong, Wenhe,Liu, Shan,Yang, Jun,Meng, Xiangbao,Li, Zhongjun
-
supporting information; experimental part
p. 3336 - 3339
(2012/08/29)
-
- Triflic acid catalyzed oxidative lactonization and diacetoxylation of alkenes using peroxyacids as oxidants
-
A clean and efficient diacetoxylation reaction of alkenes catalyzed by triflic acid using commercially available peroxyacids as the oxidants has been developed. This method was also applied in oxidative lactonizations of unsaturated carboxylic acids in good to high yields.
- Kang, Yan-Biao,Gade, Lutz H.
-
p. 1610 - 1615
(2012/04/04)
-
- BF3·OEt2-promoted diastereoselective diacetoxylation of alkenes by PhI(OAc)2
-
Selective syn and anti diacetoxylations of alkenes have been achieved using a PhI(OAc)2/BF3·OEt2 system in the presence and absence of water, respectively. A broad range of substrates including electron-deficient alkenes (such as α,β-unsaturated esters) could be elaborated efficiently at room temperature with this methodology, furnishing the desired products in good to excellent yields and diastereoselectivity. In particular, a multigram-scale diastereoselective diacetoxylation of methyl cinnamate (5.00 g) was also accomplished in a few hours, maintaining the same efficiency as small-scale reaction. This novel methodology provides an alternative approach for the preparation of various 1,2-diols.
- Zhong, Wenhe,Yang, Jun,Meng, Xiangbao,Li, Zhongjun
-
experimental part
p. 9997 - 10004
(2012/02/05)
-
- Investigation of the catalytic activity of an electron-deficient vanadium(IV) tetraphenylporphyrin: A new, highly efficient and reusable catalyst for ring-opening of epoxides
-
In this work, the catalytic activity of high-valent tetraphenylporphyrinatovanadium(IV) trifluoromethanesulfonate, [V IV(TPP)(OTf)2], in the nucleophilic ring-opening of epoxides is reported. This new V(IV) catalyst was used as an efficient catalyst for alcoholysis with primary (methanol, ethanol and n-propanol), secondary (iso-propanol) and tertiary alcohols (tert-butanol), hydrolysis and acetolysis of epoxides with acetic acid and also for the conversion of epoxides to 1,2-diacetates with acetic anhydride, conversion of epoxides to thiiranes with ammonium thiocyanate and thiourea, and for conversion of epoxides to acetonides with acetone. The catalyst was reused several times without loss of its activity.
- Taghavi, S. Abdolmanaf,Moghadam, Majid,Mohammadpoor-Baltork, Iraj,Tangestaninejad, Shahram,Mirkhani, Valiollah,Khosropour, Ahmad Reza,Ahmadi, Venus
-
experimental part
p. 2244 - 2252
(2011/10/03)
-
- The nature of the catalytically active species in olefin dioxygenation with PhI(OAc)2: Metal or proton?
-
Evidence for the protiocatalytic nature of the diacetoxylation of alkenes using PhI(OAc)2 as oxidant is presented. Systematic studies into the catalytic activity in the presence of proton-trapping and metal-complexing agents indicate that protons act as catalysts in the reaction. Using triflic acid as catalyst, the selectivity and reaction rate of the conversion is similar or superior to most efficient metal-based catalysts. Metal cations, such as Pd(II) and Cu(II), may interact with the oxidant in the initiation phase of the catalytic transformation; however, 1 equiv of strong acid is produced in the first cycle which then functions as the active catalyst. Based on a kinetic study as well as in situ mass spectrometry, a mechanistic cycle for the proton-catalyzed reaction, which is consistent with all experimental data presented in this work, is proposed.
- Kang, Yan-Biao,Gade, Lutz H.
-
supporting information; experimental part
p. 3658 - 3667
(2011/05/03)
-
- Copper-catalyzed diacetoxylation of olefins using PhI(OAc)2 as oxidant
-
(Figure Presented) Copper(I) or -(II) salts with weakly coordinating anions catalyze the diacetoxylation of olefins efficiently In the presence of PhI(OAc)2 as the oxidant under mild conditions. The reaction is effective for aryl, aryl alkyl, as well as aliphatic terminal and internal olefins forming the corresponding vicinal diacetoxy compounds In 70-85% yields and dr (syn/anti) of up to 5.2. Under these conditions, homoallylic alcohols formed the corresponding tetrahydrofuran derivatives in high yields.
- Seayad, Jayasree,Seayad, Abdul Majeed,Chai, Christina L. L.
-
supporting information; experimental part
p. 1412 - 1415
(2010/06/13)
-
- Olefin-dependent discrimination between two nonheme HO-Fev=O tautomeric species in catalytic H2O2 epoxidations
-
A study was conducted to demonstrate olefin-dependent discrimination of two nonheme HO-Fev=O tautomeric species in catalytic H2O 2 epoxidations. Mechanistic studies were carried out under the condition of excess of olefin to minimize over-oxidation reactions and all reactions for the study were carried out under a N2 atmosphere to prevent auto-oxidation process due to presence of O2. It was observed that the diol/epoxide (D/E) ration for these reaction was dependent on the specific olefin and ranged from 3/2 (cyclooctene) to 6/1 (1-octene). The oxidation of cyclooctene using H218O2 revealed that only 28% of the oxygen atoms in the epoxide derived from H 2O2. Mechanistic results suggested that HO-Fe v=O oxidant need to be labeled before its reaction with substrates.
- Company, Anna,Feng, Yan,Gueell, Mireia,Ribas, Xavi,Luis, Josep M.,Que Jr., Lawrence,Costas, Miquel
-
supporting information; experimental part
p. 3359 - 3362
(2009/12/06)
-
- Highly regioselective Pd-catalyzed intermolecular aminoacetoxylation of alkenes and evidence for cis-aminopalladation and SN2 C-O bond formation
-
Synthetic methods that achieve oxidative 1,2-difunctionalization of alkenes are very powerful in organic chemistry. Here we report the first examples of intermolecular Pd-catalyzed aminoacetoxylation of alkenes with phthalimide as the nitrogen source and PhI(OAc)2 as the stoichiometric oxidant and source of acetate. These reactions are highly regio- and diastereoselective, and mechanistic studies reveal that the reaction proceeds via cis-aminopalladation of the alkene followed by oxidative cleavage of the intermediate Pd-C bond with inversion of stereochemistry. Copyright
- Liu, Guosheng,Stahl, Shannon S.
-
p. 7179 - 7181
(2007/10/03)
-
- Aerobic oxidation of alkenes to esters of vicinal diols with a syn-configuration catalyzed by I2 and the H5PV 2Mo10O40 polyoxometalate
-
A new method for the synthesis of vicinal diols from alkenes has been developed. Reaction of molecular iodine in the presence of a polyoxometalate as oxidation catalyst under aerobic conditions in acetic acid solvent leads to the oxidative iodoacetoxylation of an alkene, i.e. formation of a 1,2-iodoacetate. Further in situ substitution of the iodide by water yields the 1,2-diol monoacetate with a predominantly (ca. 4.5:1) cis-configuration. Further esterification under the reaction's acidic conditions leads also to the cis-diacetate. The method may be valuable for the synthesis of cis-vicinal diols without use of toxic osmium catalysts. Georg Thieme Verlag Stuttgart.
- Branytska, Olena,Neumann, Ronny
-
p. 2525 - 2527
(2007/10/03)
-
- Adrenaline profiling of lipases and esterases with 1,2-diol and carbohydrate acetates
-
The adrenaline test for enzymes is a general back-titration procedure to detect 1,2-diols, 1,2-aminoalcohols and α-hydroxyketones reaction products of enzyme catalysis by colorimetry. The method was used to profile a series of esterases and lipases for their esterolytic activity on a series of carbohydrate and polyol acetates. Substrates were prepared by peracetylation and used for parallel microtiter-plate analysis of enzyme activities. This method can be used to achieve a rapid and automated characterization of a set of enzymes during HTS screening.
- Wahler, Denis,Boujard, Olivier,Lefèvre, Fabrice,Reymond, Jean-Louis
-
p. 703 - 710
(2007/10/03)
-
- Oxidation of Olefins with Benzenetelluric Anhydride
-
Olefins were found to be oxidized by use of benzenetellurinic anhydride in acetic acid leading to vic-diacetates.Benzenetellurenic acid derivatives formed in situ are suggested as the active species.This diacetoxylation proceeds in net syn fashion probably via anti acetoxytellurenylation of the olefin followed by displacement of the phenyltelluro group by an acetoxy group with inversion.
- Kambe, Nobuaki,Tsukamoto, Takashi,Miyoshi, Noritaka,Murai, Shinji,Sonoda, Noboru
-
p. 269 - 272
(2007/10/02)
-
- DOMINANT cis-DIACETOXYLATION OF ALKENES WITH TELLURIUM(IV) OXIDE AND LITHIUM BROMIDE IN ACETIC ACID
-
Oxidation of alkenes with tellurium(IV) oxide and lithium bromide in acetic acid affords the corresponding α,β-diacetoxyalkanes in good yields after acetylation of the primary products with acetic anhydride/pyridine.From cyclic alkenes such as cyclopentene, cyclohexene, cycloheptene, and 1,4-cyclohexadiene, the cis-diacetate is obtained as almost the sole product.In the cases of linear cis alkenes such as cis-2-octene and cis-4-octene cis-stereochemistry is also preferred (cis/trans = 87-89/13-11), while the proportion of the cis-product is decreased in the cases of the corresponding trans-alkenes (cis/trans = 56-58/44-42).Transformation of a C-Te bond to a C-OAc bond under these reaction conditions is shown unambiguously by using β-chloroalkyltellurium(IV) trichlorides (TeCl4 adducts of alkenes) and β-oxyalkyl phenyl tellurides (oxytellurenylation products of alkenes), cis-diacetates being solely formed from the trans-tellurium compounds in a cyclohexyl system.One of the possible reaction patways for the oxidation is proposed which involves the acetoxy-, hydroxy-, and/or halogeno-tellurinylation of a double bond followed by an SN2 type acetolysis of the produced C-Te bond.
- Uemura, Sakae,Ohe, Kouichi,Fukuzawa, Shin-Ichi,Patil, Suresh R.,Sugita, Nobuyuki
-
-
- ALKENE OXIDATION BY AN IRON(II)/PERSULFATE/ACETIC ACID SYSTEM
-
Mono- and disubstituted alkenes were converted to trans-vicinal diacetates by heating with an iron(II)/persulfate/acetic acid system.The synthetic utility and limitations were identified.A mechanism for the transformation is proposed wich involves an initial addition of sulfate radical anion to the alkene followed by solvolysis, addition, hydrolysis, and acetylation.
- Fristad, William E.,Peterson, John R.
-
p. 1469 - 1476
(2007/10/02)
-
- IRON(II) CATALYZED ODIDATION OF ALKENES TO VICINAL DIACETATES
-
Mono- and disubstituted alkenes are converted to trans-vicinal diacetates by heating with an acetic acid solution of ammonium persulfate and a ferrous sulfate catalyst.
- Fristad, William E.,Peterson, John R.
-
p. 4547 - 4550
(2007/10/02)
-
- PREPARATION OF 1,3-DIOLS BY METALATION-HYDROBORATION OF ALKYNES A 1,2-HYDROGEN MIGRATION FROM BORON TO CARBON
-
Metalation of a series of 1- and 2-alkynes with subsequent treatment with diborane and oxidation gave 1,3-diols exclusively.Deuteroboration of the lithiated acetylenes established the occurrence of a displacement of one of the B atoms by deuterium in gem-diboronated compounds.Hydroboration of several acetylenes and acetylides was also studied.
- Medlik-Balan, A.,Klein, J.
-
p. 299 - 304
(2007/10/02)
-