共查询到20条相似文献,搜索用时 15 毫秒
1.
Dr. Xinjiang Cui Dr. Yuehui Li Dr. Christoph Topf Dr. Kathrin Junge Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2015,54(36):10596-10599
The “green” reduction of carboxylic acids to alcohols is a challenging task in organic chemistry. Herein, we describe a general protocol for generation of alcohols by catalytic hydrogenation of carboxylic acids. Key to success is the use of a combination of Ru(acac)3, triphos and Lewis acids. The novel method showed broad substrate tolerance and a variety of aliphatic carboxylic acids including biomass‐derived compounds can be smoothly reduced. 相似文献
2.
Jenny Wettergren Dr. Elina Buitrago Per Ryberg Dr. Hans Adolfsson Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(23):5709-5718
Lithium‐powered : A kinetic investigation into the asymmetric transfer hydrogenation of non‐activated aryl alkyl ketones, catalyzed by N‐Boc‐protected α‐amino acid hydroxyamide ruthenium–arene complexes, has revealed that the reactions proceed through an unprecedented bimetallic outer‐sphere mechanism. Under optimized conditions, these catalysts provide access to secondary alcohols in high yields and with excellent enantioselectivities (>99 % ee).
3.
Guo Bin SUN Wei Wei PEI* Hui WANG Wei Ping YE College of Chemistry Molecular Engineering Peking University Beijing 《中国化学快报》2002,13(12)
The catalytic enantioselective borane reduction of ketones is a well-studied theme1. Since the pioneering work of Corey2, a variety of good catalysts have been synthesized through further modification on simple amino alcohols and their corresponding amino acids,3,4 . But when simple amino alcohols were directly used in the reduction their catalytic efficiency was very low. For the first time Buono5 has reported through carefully chosen reaction condition the catalytic efficiency of a simple… 相似文献
4.
Saravanakumar Elangovan Marcel Garbe Dr. Haijun Jiao Dr. Anke Spannenberg Dr. Kathrin Junge Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2016,55(49):15364-15368
The first manganese‐catalyzed hydrogenation of esters to alcohols has been developed. The combination of Mn(CO)5Br with [HN(CH2CH2P(Et)2)2] leads to a mixture of cationic and neutral Mn PNP pincer complexes, which enable the reduction of various ester substrates, including aromatic and aliphatic esters as well as diesters and lactones. Notably, related pincer complexes with isopropyl or cyclohexyl substituents showed very low activity. 相似文献
5.
6.
Phenylalanine Ammonia Lyase Catalyzed Synthesis of Amino Acids by an MIO‐Cofactor Independent Pathway 下载免费PDF全文
Sarah L. Lovelock Dr. Richard C. Lloyd Prof. Nicholas J. Turner 《Angewandte Chemie (International ed. in English)》2014,53(18):4652-4656
Phenylalanine ammonia lyases (PALs) belong to a family of 4‐methylideneimidazole‐5‐one (MIO) cofactor dependent enzymes which are responsible for the conversion of L ‐phenylalanine into trans‐cinnamic acid in eukaryotic and prokaryotic organisms. Under conditions of high ammonia concentration, this deamination reaction is reversible and hence there is considerable interest in the development of PALs as biocatalysts for the enantioselective synthesis of non‐natural amino acids. Herein the discovery of a previously unobserved competing MIO‐independent reaction pathway, which proceeds in a non‐stereoselective manner and results in the generation of both L ‐ and D ‐phenylalanine derivatives, is described. The mechanism of the MIO‐independent pathway is explored through isotopic‐labeling studies and mutagenesis of key active‐site residues. The results obtained are consistent with amino acid deamination occurring by a stepwise E1cB elimination mechanism. 相似文献
7.
8.
Svenja Werkmeister Dr. Kathrin Junge Bianca Wendt Dr. Elisabetta Alberico Dr. Haijun Jiao Dr. Wolfgang Baumann Dr. Henrik Junge Dr. Fabrice Gallou Prof. Dr. Matthias Beller 《Angewandte Chemie (International ed. in English)》2014,53(33):8722-8726
We present the first base‐free Fe‐catalyzed ester reduction applying molecular hydrogen. Without any additives, a variety of carboxylic acid esters and lactones were hydrogenated with high efficiency. Computations reveal an outer‐sphere mechanism involving simultaneous hydrogen transfer from the iron center and the ligand. This assumption is supported by NMR experiments. 相似文献
9.
Rhodium‐Catalyzed Asymmetric Hydrogenation of Unprotected NH Imines Assisted by a Thiourea 下载免费PDF全文
Qingyang Zhao Jialin Wen Renchang Tan Kexuan Huang Pedro Metola Prof. Rui Wang Prof. Eric V. Anslyn Prof. Xumu Zhang 《Angewandte Chemie (International ed. in English)》2014,53(32):8467-8470
Asymmetric hydrogenation of unprotected NH imines catalyzed by rhodium/bis(phosphine)‐thiourea provided chiral amines with up to 97 % yield and 95 % ee. 1H NMR studies, coupled with control experiments, implied that catalytic chloride‐bound intermediates were involved in the mechanism through a dual hydrogen‐bonding interaction. Deuteration experiments proved that the hydrogenation proceeded through a pathway consistent with an imine. 相似文献
10.
Katrin Ahlford Jesper Ekström Dr. Alexey B. Zaitsev Dr. Per Ryberg Dr. Lars Eriksson Dr. Hans Adolfsson Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(42):11197-11209
Amino acid based thioamides, hydroxamic acids, and hydrazides have been evaluated as ligands in the rhodium‐catalyzed asymmetric transfer hydrogenation of ketones in 2‐propanol. Catalysts containing thioamide ligands derived from L ‐valine were found to selectively generate the product with an R configuration (95 % ee), whereas the corresponding L ‐valine‐based hydroxamic acids or hydrazides facilitated the formation of the (S)‐alcohols (97 and 91 % ee, respectively). The catalytic reduction was examined by performing a structure–activity correlation investigation with differently functionalized or substituted ligands and the results obtained indicate that the major difference between the thioamide and hydroxamic acid based catalysts is the coordination mode of the ligands. Kinetic experiments were performed and the rate constants for the reduction reactions were determined by using rhodium–arene catalysts derived from amino acid thioamide and hydroxamic acid ligands. The data obtained show that the thioamide‐based catalyst systems demonstrate a pseudo‐first‐order dependence on the substrate, whereas pseudo‐zero‐order dependence was observed for the hydroxamic acid containing catalysts. Furthermore, the kinetic experiments revealed that the rate‐limiting steps of the two catalytic systems differ. From the data obtained in the structure–activity correlation investigation and along with the kinetic investigation it was concluded that the enantioswitchable nature of the catalysts studied originates from different ligand coordination, which affects the rate‐limiting step of the catalytic reduction reaction. 相似文献
11.
Tsukuru Maeda Dr. Kazuishi Makino Masamichi Iwasaki Prof. Yasumasa Hamada 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(39):11954-11962
The development of Ir‐catalyzed asymmetric hydrogenation of α‐amino‐β‐keto ester hydrochlorides is described. This reaction proceeds through a dynamic kinetic resolution to produce anti‐β‐hydroxy‐α‐amino acid esters in a high diastereo‐ and enantioselective manner. Mechanistic studies have revealed that this unique asymmetric hydrogenation proceeds through reduction of the ketone moiety via the five‐membered transition state involving the chelation between the oxygen of the ketone and the nitrogen of the amine function. The relationship studies between the hydrogen pressure and the stereoselectivity have disclosed two mechanisms dependent on hydrogen pressure. Under low hydrogen pressure (<15 atm), the reaction rate proportionally increased with the hydrogen pressure. However, under the high hydrogen conditions, the reaction rate exponentially accelerated along with the increasing hydrogen pressure, which suggests the participation of two or more of hydrogen atoms. 相似文献
12.
Christos Raptis Hermenegildo Garcia Prof. Dr. Manolis Stratakis Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(17):3133-3136
ReacTiO 2 ns for rings : Gold nanoparticles supported on TiO2 are used as a novel heterogeneous catalyst for the isomerization of epoxides to allylic alcohols by a concerted mechanism (see scheme). The reaction proceeds in high yields and the product selectivity is often remarkable.
13.
Kseniya Revunova Dr. Georgii I. Nikonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(3):839-845
Simple bases (KOtBu, KOH) catalyze the silane‐promoted reduction of ketones and esters to alcohols and of aldimines to amines. The inexpensive silane PMHS (polymethylhydrosiloxane) can be used as the reducing reagent. Double and triple bonds, as well as nitro‐ and cyano‐groups are tolerated. Careful dosing of the silane allows for chemoselective reduction of a more reactive group in the presence of a less reactive group (for example, aldehyde reduction in the presence of ketone/ketone reduction in the presence of ester group). Mechanistic studies showed that addition of base to silanes leads to silicate species, which are the acting reducing agents. Under basic conditions, hydrosiloxanes (tetramethyldisiloxane, TMDS; PMHS) convert into simple silanes (H2SiMe2, H3SiMe), making this a practical method to generate these challenging silanes. 相似文献
14.
15.
16.
Ruthenium-Catalyzed Deaminative Hydrogenation of Amino Nitriles: Direct Access to 1,2-Amino Alcohols
Dr. Pilar Calleja Dr. Martin Ernst Prof. Dr. A. Stephen K. Hashmi Dr. Thomas Schaub 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(40):9498-9503
A new approach for the efficient and highly selective synthesis of 1,2-amino alcohols by direct reductive hydrolysis of N-formyl-protected α-amino nitriles is reported. The commercially available RuHCl(CO)(PPh3)3 complex was found to be a suitable catalyst for this operationally simple protocol, in which no stoichiometric amounts of undesired metal waste are generated. The deaminative hydrogenation is performed at 55 bar of H2, using a 6:1 mixture of 1,4-dioxane/water as solvent. In addition, hydroxymethyl alcohols were prepared from cyanoketones under very similar conditions. 相似文献
17.
Iridium‐Catalyzed Enantioselective Hydrogenation of Oxocarbenium Ions: A Case of Ionic Hydrogenation
Tilong Yang Yongjie Sun Heng Wang Zhenyang Lin Jialin Wen Xumu Zhang 《Angewandte Chemie (International ed. in English)》2020,59(15):6108-6114
Ionic hydrogenation has not been extensively explored, but is advantageous for challenging substrates such as unsaturated intermediates. Reported here is an iridium‐catalyzed hydrogenation of oxocarbenium ions to afford chiral isochromans with high enantioselectivities. A variety of functionalities are compatible with this catalytic system. In the presence of a catalytic amount of the Brønsted acid HCl, an α‐chloroether is generated in situ and subsequentially reduced. Kinetic studies suggest first‐order kinetics in the substrate and half‐order kinetics in the catalyst. A positive nonlinear effect, together with the half kinetic order, revealed a dimerization of the catalyst. Possible reaction pathways based on the monomeric iridium catalyst were proposed and DFT computational studies revealed an ionic hydrogenation pathway. Chloride abstraction and the cleavage of dihydrogen occur in the same step. 相似文献
18.
A highly efficient palladium‐catalyzed direct coupling of propargylic alcohols with organoboronic acids to synthesize tri‐ and tetra‐substituted allenes has been developed under mild reaction conditions. Many useful functional groups are tolerated in this process with high to excellent yields. Preliminary biological studies showed that several tri‐ and tetra‐substituted allenes exhibited potent anti‐diabetic activities. 相似文献
19.
Mechanistic Insights into the Pd‐Catalyzed Direct Amination of Allyl Alcohols: Evidence for an Outer‐Sphere Mechanism Involving a Palladium Hydride Intermediate 下载免费PDF全文
Supaporn Sawadjoon Dr. Per J. R. Sjöberg Dr. Andreas Orthaber Prof. Olle Matsson Dr. Joseph S. M. Samec 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1520-1524
The mechanism of direct amination of allyl alcohol by a palladium triphenylphosphite complex has been explored. Labelling studies show that the reaction proceeds through a π‐allylpalladium intermediate. A second‐order dependence of reaction rate on allyl alcohol concentration was observed. Kinetic isotope effect studies and ESI‐MS studies are in agreement with a reaction proceeding through a palladium hydride intermediate in which both O–H bond and C–O bond cleavages are involved in rate‐determining steps. A stereochemical study supports an outer‐sphere nucleophilic attack of the π‐allylpalladium intermediate giving complete chiral transfer from starting material to product. 相似文献
20.
Jeroen Wassenaar Mark Kuil Dr. Martin Lutz Dr. Anthony L. Spek Prof. Dr. Joost N. H. Reek Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(22):6509-6517
The mechanism of the IndolPhos–Rh‐catalyzed asymmetric hydrogenation of prochiral olefins has been investigated by means of X‐ray crystal structure determination, kinetic measurements, high‐pressure NMR spectroscopy, and DFT calculations. The mechanistic study indicates that the reaction follows an unsaturate/dihydride mechanism according to Michaelis–Menten kinetics. A large value of KM (KM=5.01±0.16 M ) is obtained, which indicates that the Rh–solvate complex is the catalyst resting state, which has been observed by high‐pressure NMR spectroscopy. DFT calculations on the substrate–catalyst complexes, which are undetectable by experimental means, suggest that the major substrate–catalyst complex leads to the product. Such a mechanism is in accordance with previous studies on the mechanism of asymmetric hydrogenation reactions with C1‐symmetric heteroditopic and monodentate ligands. 相似文献