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1.
Teng Wei Ng Gang Liao Kai Kiat Lau Hui-Jie Pan Prof. Dr. Yu Zhao 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(28):11480-11485
We report herein an unprecedented highly efficient Guerbet-type reaction at room temperature (catalytic TON up to >6000). This β-alkylation of secondary methyl carbinols with primary alcohols has significant advantage of delivering higher-order secondary alcohols in an economical, redox-neutral fashion. In addition, the first enantioselective Guerbet reaction has also been achieved using a commercially available chiral ruthenium complex to deliver secondary alcohols with moderate yield and up to 92 % ee. In both reactions, the use of a traceless ketone promoter proved to be beneficial for the catalytic efficiency. 相似文献
2.
Kun Wang Lin Zhang Weijun Tang Huaming Sun Dong Xue Ming Lei Jianliang Xiao Chao Wang 《Angewandte Chemie (International ed. in English)》2020,59(28):11408-11415
The first example of an asymmetric Guerbet reaction has been developed. Using commercially available, classic Noyori RuII‐diamine‐diphosphine catalysts, well‐known in asymmetric hydrogenation, racemic secondary alcohols are shown to couple with primary alcohols in the presence of a base, affording new chiral alcohols with enantiomeric ratios of up to 99:1. Requiring no reducing agents, the protocol provides an easy, alternative route for the synthesis of chiral alcohols. Mechanistic studies reveal that the reaction proceeds via a Ru‐catalyzed asymmetric hydrogen autotransfer process in concert with a base‐promoted allylic alcohol isomerization. 相似文献
3.
The solvent‐free O‐acylation of some alcohols with benzoyl chloride was carried out to the corresponding benzoylated products in good to excellent yields by the mediation of a catalytic amount (5 mol%) of the commercially available and inexpensive zinc oxide in short reaction times. This methodology represents an eco‐friendly and simple catalytic alternative for benzoylation of primary, secondary, tertiary, and benzylic alcohols with ZnO. This catalytic system was homogeneous because of high solubility of zinc oxide in the reaction medium. Findings showed that ZnO was dissolved in hydrochloric acid, created in situ, after a few minutes. Although, others argued on the catalytic role of solid phase zinc oxide under a heterogeneous condition, it is not surprising to emphasize on the catalytic function of Zn2+ in the benzoylation of alcohols under homogeneous reaction conditions. Zinc oxide served as pre‐catalyst to form Zn2+, as the catalytically active species. 相似文献
4.
Abdolreza Rezaeifard Maasoumeh Jafarpour Mohammad Ali Nasseri Reza Haddad 《Helvetica chimica acta》2010,93(4):711-717
A novel and practical catalytic method for efficient and highly selective oxidation of a wide range of benzylic, allylic, aliphatic, primary, and secondary alcohols to the corresponding aldehydes and ketones using tetrabutylammonium peroxomonosulfate catalyzed by tetradentate Schiff base–MnIII complexes has been developed. Electron‐deficient and hindered alcohols required longer reaction times for oxidation in this catalytic system. The electron‐poor and hindered salicylidene ring of the ligand enhanced the catalytic activity and stability of Mn catalysts. The desired turnover numbers obtained in the oxidation reactions indicated the high efficiency and relative stability of these simple Schiff base complexes in this catalytic system. 相似文献
5.
Selective tetrahydropyranylation of alcohols and phenols using titanium(IV) salophen trifluoromethanesulfonate as an efficient catalyst 下载免费PDF全文
Titanium(IV) salophen trifluoromethanesulfonate, [TiIV(salophen)(OSO2CF3)2], as a catalyst enables selective tetrahydropyranylation of alcohols and phenols with 3,4‐dihydro‐2H‐pyran. Using this catalytic system, primary, secondary and tertiary alcohols, as well as phenols, were converted to their corresponding tetrahydropyranyl ethers in high yields and short reaction times at room temperature. Investigation of the chemoselectivity of this method showed discrimination between the activity of primary alcohols in the presence of secondary and tertiary alcohols and phenols. This heterogenized catalyst could be reused several times without loss of its catalytic activity. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
6.
Asymmetric Ring‐Opening of Cyclopropyl Ketones with Thiol,Alcohol, and Carboxylic Acid Nucleophiles Catalyzed by a Chiral N,N′‐Dioxide–Scandium(III) Complex 下载免费PDF全文
Yong Xia Dr. Lili Lin Fenzhen Chang Xuan Fu Prof. Dr. Xiaohua Liu Prof. Dr. Xiaoming Feng 《Angewandte Chemie (International ed. in English)》2015,54(46):13748-13752
A highly efficient asymmetric ring‐opening reaction of cyclopropyl ketones with a broad range of thiols, alcohols and carboxylic acids has been first realized by using a chiral N,N′‐dioxide–scandium(III) complex as catalyst. The corresponding sulfides, ethers, and esters were obtained in up to 99 % yield and 95 % ee. This is also the first example of one catalytic system working for the ring‐opening reaction of donor–acceptor cyclopropanes with three different nucleophiles, let alone in an asymmetric version. 相似文献
7.
Meng Sun Chun Ma Si‐Jia Zhou Sai‐Fan Lou Jian Xiao Yinchun Jiao Feng Shi 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(26):8795-8800
The first catalytic asymmetric (4+3) cyclization of in situ generated ortho‐quinone methides with 2‐indolylmethanols has been established, which constructed seven‐membered heterocycles in high yields (up to 95 %) and excellent enantioselectivity (up to 98 %). This approach not only represents the first catalytic asymmetric (4+3) cyclization of o‐hydroxybenzyl alcohols, but also enabled an unprecedented catalytic asymmetric (4+3) cyclization of 2‐indolylmethanols. In addition, a scarcely reported catalytic asymmetric (4+3) cyclization of para‐quinone methide derivatives was accomplished. 相似文献
8.
Yong Xia Lili Lin Fenzhen Chang Xuan Fu Xiaohua Liu Xiaoming Feng 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(46):13952-13956
A highly efficient asymmetric ring‐opening reaction of cyclopropyl ketones with a broad range of thiols, alcohols and carboxylic acids has been first realized by using a chiral N,N′‐dioxide–scandium(III) complex as catalyst. The corresponding sulfides, ethers, and esters were obtained in up to 99 % yield and 95 % ee. This is also the first example of one catalytic system working for the ring‐opening reaction of donor–acceptor cyclopropanes with three different nucleophiles, let alone in an asymmetric version. 相似文献
9.
Yusuke Shimada Yoshihiro Miyake Dr. Hiroshi Matsuzawa Dr. Yoshiaki Nishibayashi Prof. Dr. 《化学:亚洲杂志》2007,2(3):393-396
The deracemization of secondary benzylic alcohols proceeds successfully by a two‐step process with the appropriate combination of two different ruthenium complexes for catalysis in the first oxidation and second reduction steps. The sequential catalytic system provides a novel approach to obtaining optically active alcohols, including diols, in high yields with excellent enantioselectivity (up to 95 % ee), in contrast to the conventional kinetic resolution of racemic alcohols. 相似文献
10.
Efficient ruthenium‐, rhodium‐, palladium‐, copper‐ and iridium‐catalysed methodologies have been recently developed for the synthesis of quinolines by the reaction of 2‐aminobenzyl alcohols with carbonyl compounds (aldehydes and ketones) or the related alcohols. The reaction is assumed to proceed via a sequence involving initial metal‐catalysed oxidation of 2‐aminobenzyl alcohols to the related 2‐aminobenzaldehydes, followed by cross aldol reaction with a carbonyl compound under basic conditions to afford α,β‐unsaturated carbonyl compounds. These aldehydes or ketones can be also generated in situ via dehydrogenation of the related primary and secondary alcohols. In the final step cyclodehydration of the α,β‐unsaturated carbonyl compound intermediates gives quinolines. Good yields of quinolines were also obtained by reacting 2‐nitrobenzyl alcohols and secondary alcohols in the presence of a ruthenium catalyst. Finally, aniline derivatives afforded also a useful access to quinolines by the reaction with 1,3‐propanediol or 3‐amino‐1‐propanol, or in a three‐component reaction with benzyl alcohol and aliphatic alcohols. 相似文献
11.
Qingzhu Zou Prof. Dr. Chao Wang Jen Smith Prof. Dr. Dong Xue Prof. Dr. Jianliang Xiao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(27):9656-9661
An efficient catalytic system for the alkylation of amines with either alcohols or amines under mild conditions has been developed, using cyclometallated iridium complexes as catalysts. The method has broad substrate scope, allowing for the synthesis of a diverse range of secondary and tertiary amines with good to excellent yields. By controlling the ratio of substrates, both mono‐ and bis‐alkylated amines can be obtained with high selectivity. In particular, methanol can be used as the alkylating reagent, affording N‐methylated products selectively. A strong solvent effect is observed for the reaction. 相似文献
12.
Selective oxidation of alcohols to corresponding carbonyl compounds is one of the most important processes both in academic and application research. As a kind of biomimetic catalyst, metalloporphyrins‐catalyzed aerobic oxidation of alcohols with aldehyde as hydrogen donator is gathering much attention. However, using olefins as another kind hydrogen donator for aerobic oxidation of alcohols has not been reported. In this study, a system comprising managenese porphyrin and cyclohexene for biomimetic aerobic oxidation of alcohols to carbonyl compounds was developed. The catalytic system exhibited excellent catalytic performance and selectivity towards the corresponding products for most primary and secondary alcohols under mild conditions. Based on the results obtained from experiments as well as in situ EPR (electron paramagnetic resonance) and UV‐vis spectroscopy, the role of cyclohexene was demonstrated. 相似文献
13.
ZnCl2‐Promoted Asymmetric Hydrogenation of β‐Secondary‐Amino Ketones Catalyzed by a P‐Chiral Rh–Bisphosphine Complex 下载免费PDF全文
Qiupeng Hu Dr. Zhenfeng Zhang Prof. Yangang Liu Prof. Tsuneo Imamoto Prof. Wanbin Zhang 《Angewandte Chemie (International ed. in English)》2015,54(7):2260-2264
A new catalytic system has been developed for the asymmetric hydrogenation of β‐secondary‐amino ketones using a highly efficient P‐chiral bisphosphine–rhodium complex in combination with ZnCl2 as the activator of the catalyst. The chiral γ‐secondary‐amino alcohols were obtained in 90–94 % yields, 90–99 % enantioselectivities, and with high turnover numbers (up to 2000 S/C; S/C=substrate/catalyst ratio). A mechanism for the promoting effect of ZnCl2 on the catalytic system has been proposed on the basis of NMR spectroscopy and HRMS studies. This method was successfully applied to the asymmetric syntheses of three important drugs, (S)‐duloxetine, (R)‐fluoxetine, and (R)‐atomoxetine, in high yields and with excellent enantioselectivities. 相似文献
14.
Asymmetric Hydroalkoxylation of Non‐Activated Alkenes: Titanium‐Catalyzed Cycloisomerization of Allylphenols at High Temperatures 下载免费PDF全文
M. Sc. Johannes Schlüter M. Sc. Max Blazejak Dr. Florian Boeck Prof. Dr. Lukas Hintermann 《Angewandte Chemie (International ed. in English)》2015,54(13):4014-4017
The asymmetric catalytic addition of alcohols (phenols) to non‐activated alkenes has been realized through the cycloisomerization of 2‐allylphenols to 2‐methyl‐2,3‐dihydrobenzofurans (2‐methylcoumarans). The reaction was catalyzed by a chiral titanium–carboxylate complex at uncommonly high temperatures for asymmetric catalytic reactions. The catalyst was generated by mixing titanium isopropoxide, the chiral ligand (aS)‐1‐(2‐methoxy‐1‐naphthyl)‐2‐naphthoic acid or its derivatives, and a co‐catalytic amount of water in a ratio of 1:1:1 (5 mol % each). This homogeneous thermal catalysis (HOT‐CAT) gave various (S)‐2‐methylcoumarans with yields of up to 90 % and in up to 85 % ee at 240 °C, and in 87 % ee at 220 °C. 相似文献
15.
Carlo Carlini Marco Di Girolamo Alessandro Macinai Mario Marchionna Marilena Noviello Anna Maria Raspolli Galletti Glauco Sbrana 《Journal of molecular catalysis. A, Chemical》2003,200(1-2):137-146
The synthesis of isobutanol via the Guerbet condensation between methanol and ethanol was studied by using sodium methoxide (MeONa) as soluble basic component and copper-based catalysts as heterogeneous dehydrogenating/hydrogenating metal species. The effect of the nature of the catalyst and the relative amount of its individual components with respect to the reacting alcohols as well as of temperature on productivity and selectivity of the process was investigated. The collected data indicated that the copper chromite/MeONa was more active than Cu-Raney/MeONa system. The reaction was shown to proceed with the formation only of n-propanol and isobutanol. Ethanol conversion up to 61% with selectivity to isobutanol up to 98.4% was obtained. The same catalytic systems were also employed in the reaction of the methanol/ethanol/n-propanol ternary mixture. Again copper chromite/MeONa resulted more active than the Cu-Raney/MeONa system. Finally, experiments were carried out on methanol/n-propanol mixtures in the presence of the copper chromite/MeONa catalytic system by recycling both the recovered solid copper component and the liquid reaction mixture for evidencing eventual copper leaching by MeONa. On the basis of the obtained results it was concluded that in the Guerbet reaction copper chromite works as heterogeneous catalyst. 相似文献
16.
Phosphoric Acid Catalyzed Desymmetrization of Bicyclic Bislactones Bearing an All‐Carbon Stereogenic Center: Total Syntheses of (−)‐Rhazinilam and (−)‐Leucomidine B 下载免费PDF全文
Jean‐Baptiste Gualtierotti Delphine Pasche Dr. Qian Wang Prof. Dr. Jieping Zhu 《Angewandte Chemie (International ed. in English)》2014,53(37):9926-9930
In the presence of a catalytic amount of an imidodiphosphoric acid, enantioselective desymmetrization of bicyclic bislactones by reaction with alcohols took place smoothly to afford enantiomerically enriched monoacids having an all‐carbon stereogenic center. Concise catalytic enantioselective syntheses of both (?)‐rhazinilam and (?)‐leucomidine B were subsequently developed using (S)‐methyl 4‐ethyl‐4‐formylpimelate monoacid as a common starting material. 相似文献
17.
Majid Moghadam Shahram Tangestaninejad Valiollah Mirkhani Iraj Mohammadpoor‐Baltork Shadab Gharaati 《应用有机金属化学》2009,23(11):446-454
In this paper, rapid and highly efficient trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) in the presence of catalytic amounts of high‐valent [SnIV(TPP)(OTf)2] is reported. This catalytic system catalyzes trimethylsilylation of primary, secondary and tertiary alcohols as well as phenols, and the corresponding TMS‐ethers were obtained in high yields and short reaction times at room temperature. It is noteworthy that this method can be used for chemoselective silylation of primary alcohols in the presence of secondary and tertiary alcohols and phenols. The catalyst was reused several times without loss of its catalytic activity. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
18.
A variety of aromatic, aliphatic and conjugated aldehydes and alcohols were transformed to the corresponding carboxylic acids and ketones with a quantitative conversion in high yields with 70% t‐BuOOH solution in water in the presence of catalytic (5 mol%) amounts of CuBr2 under room temperature conditions. The conversion of 4‐methoxybenzaldehyde to 4‐methoxybenzoic acid is extremely facile in MeCN at ambient temperature in the presence of 5 mol% CuBr2 and 2 equiv. 70% t‐BuOOH (water) as the oxidant. Oxidation with t‐BuOOH (water) alone in MeCN was found to be negligible. The scope of our catalytic system is applicable for a wide range of aromatic, conjugated and aliphatic substrates. These aldehydes were converted to the corresponding carboxylic acids in good isolated yields in reasonable times. It is pertinent to mention here that mild halogenic oxidants like hypochlorites, chlorites and NBS are not suitable for substrates with electron‐rich aromatic rings, olefinic bonds and secondary hydroxyl groups. Substitutions at different positions on the phenyl ring do not hinder the reaction, although the reaction time is affected. Oxidation of α,β unsaturated derivatives resulted in the formation of the expected acid in good yield. In addition, the transformation of secondary alcohols to ketones is extremely facile. No recemization was observed for menthone. This method possesses a wide range of capabilities since it can be used with other functional groups which may not tolerate oxidative conditions, involves fairly simple method for work‐up, exhibits chemoselectivity and proceeds under ambient conditions. The resulting products are obtained in good yields within reasonable time. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
19.
Catalytic Asymmetric Inverse‐Electron‐Demand Oxa‐Diels–Alder Reaction of In Situ Generated ortho‐Quinone Methides with 3‐Methyl‐2‐Vinylindoles 下载免费PDF全文
Jia‐Jia Zhao Si‐Bing Sun Sai‐Huan He Dr. Qiong Wu Prof. Dr. Feng Shi 《Angewandte Chemie (International ed. in English)》2015,54(18):5460-5464
The first catalytic asymmetric inverse‐electron‐demand (IED) oxa‐Diels–Alder reaction of ortho‐quinone methides, generated in situ from ortho‐hydroxybenzyl alcohols, has been established. By selecting 3‐methyl‐2‐vinylindoles as a class of competent dienophiles, this approach provides an efficient strategy to construct an enantioenriched chroman framework with three adjacent stereogenic centers in high yields and excellent stereoselectivities (up to 99 % yield, >95:5 d.r., 99.5:0.5 e.r.). The utilization of ortho‐hydroxybenzyl alcohols as precursors of dienes and 3‐methyl‐2‐vinylindoles as dienophiles, as well as the hydrogen‐bonding activation mode of the substrates met the challenges of a catalytic asymmetric IED oxa‐Diels–Alder reaction. 相似文献
20.
Subramani Rajkumar Mengyao Tang Xiaoyu Yang 《Angewandte Chemie (International ed. in English)》2020,59(6):2333-2337
An efficient method for the asymmetric synthesis of 4H‐3,1‐benzoxazines was developed by kinetic resolution of 2‐amido benzyl alcohols using chiral phosphoric acid catalyzed intramolecular cyclizations. A broad range of benzyl alcohols (both secondary and tertiary alcohols) were kinetically resolved with high selectivities, with an s factor of up to 94. Mechanistic studies were performed to elucidate the mechanism of these reactions, wherein the amide moieties reacted as the electrophiles. Gram‐scale reaction and facile transformations of the chiral products demonstrate the potential of this method in asymmetric synthesis of biologically active chiral heterocycles. 相似文献