In response to these problems, stuart warren and coworkers employed similar reaction conditions to the sharpless asymmetric dihydroxylation, but replacing the chiral ligands with the achiral quinuclidine to give a racemic reaction product assuming an achiral starting material is employed. Catalytic asymmetric dihydroxylation of alkenes aims of the experiment to prepare an enantiomerically enriched 1,2diol using sharpless catalytic asymmetric dihydroxylation procedure, and to estimate the enantiomeric purity of the material you. The steps involve a highly enantioselective sharpless asymmetric dihydroxylation of. General characteristics sharpless developed chiral ligands dhqd2phal or dhq2phal derived from cinchona alkaloids quinidine, quinine for the practical osmium tetroxidecatalyzed asymmetric dihydroxylation reaction. Sources of free radicals can cause runaway polymerisation. Enzymatic dihydroxylation of aromatics in enantioselective synthesis. Accurate prediction of experimental free energy of activation barriers for the. Sharpless asymmetric dihydroxylation continued youtube. Myers sharpless asymmetric dihydroxylation reaction chem 115 sharpless asymmetric dihydroxylation reaction chem 115 h n dhq c. The journal of organic chemistry 2011, 76 20, 85548559.
Attain mastery in predicting the product for this reaction. A new ligand class for the asymmetric dihydroxylation of olefins. Enantioselective cis dihydroxylation of olefins using osmium catalyst in the presence of cinchona alkaloid ligands. Asymmetric dihydroxylation of esters and amides of. The selection of dihydroquinidine dhqd or dihydroquinine dhq as a chiral auxiliary. Sharpless asymmetric dihydroxylation of olefins in. For more than 50 years, the accepted opinion was that the dihydroxylation of olefins with oso4 proceeded by a concerted mechanism eq. Experimental and theoretical kinetic isotope effects for. Asymmetric dihydroxylation kolb, hartmuth c sharpless, k. Because the sharpless dihydroxylation occurs with greater selectivity for transdouble bonds, we selected 2z,4edienoate 6 to study. Nonracemic lactones from the sharpless asymmetric dihydroxylation of. However, there are limitations to performing the catalytic ad reaction on a large scale due to the toxicity of osmium tetroxide and the high cost of preparing the cinchona alkaloid ligands.
Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all. Barry sharpless to use catalytic amounts of oso 4 along with the stoichiometric oxidant k 3 fecn 6. Multigramme synthesis and asymmetric dihydroxylation of a 4. This reaction is a transformation of olefins into syn. Files are available under licenses specified on their description page. However, users may print, download, or email articles for individual use.
Barry sharples s nikki goodwin macmillan group meeting august 28, 2002 sharpless asymmetric epoxidation i. Multigramme synthesis and asymmetric dihydroxylation of a. Since sharpless discovery of the asymmetric dihydroxylation of cc double bonds in the late 1980s this reaction has become a powerful tool. Sharpless asymmetric dihydroxylation is the chemical reaction of an alkene with osmium tetroxide in the presence of a chiral quinine ligand to form a vicinal diol. Electrochemical oscatalyzed asymmetric dihydroxylation of. The prominent advantage of the electrooxidation method is that minimum use of reoxidizing agent as well as k 2 oso 2 oh 4 may cause to improve. Sharpless asymmetric dihydroxylation also called the sharpless bishydroxylation is the chemical reaction of an alkene with osmium tetroxide in the presence of a chiral quinine ligand to form a vicinal diol. A phase transfer catalysed fluorination transformed these species to the 4fluorobut2eenoates reproducibly and at scale 4853%, ca. Inorganic chemistry organic chemistry nobel prize cinchona alkaloid asymmetric dihydroxylation these keywords were added by machine and not by the authors. Optically active cinchona alkaloid was anchored onto mesoporous sba16 silica and the asprepared complex was used as a heterogeneous chiral ligand of osmium tetraoxide for the asymmetric dihydroxylation of olefins. University of groningen cisdihydroxylation and epoxidation. Literature findings on the facial selectivity of the sharpless asymmetric dihydroxylation sad of isobutyl angelate are contradictory and partly in conflict with the sharpless mnemonic. Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinated c 4 building block at high enantiomericenrichment.
In 1980, the first attempt for enantioselective cis dihydroxylation of alkenes with osmium tetroxide was appeared. Jm chong and kb sharpless nucleophilic opening of 23 epoxy. While nmo is also a viable reagent as the reoxidant, the use of potassium ferricyanide. In many cases excellent regioselectivities are obtained. We systematically screened the sad of esters and amides of angelic, tiglic, and methacrylic acid. Sharpless asymmetric dihydroxylation springerlink skip to main content. Part of thebiochemistry commons, and thechemistry commons this dissertation is brought to you for free and open access by byu scholarsarchive. The ordered mesoporous sba16 silica was found to be a valuable support. Esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. While highly efficient catalytic kinetic resolutions by means of the classical sharpless asymmetric epoxidation ae reactions are well established in modern organic synthesis, such systems based on the arguably more versatile sharpless asymmetric dihydroxylation ad processes, although long pursued and widely attempted, remain largely. Asymmetric dihydroxylation reactions were then used to transform the butenoate, ultimately into all four diastereoisomers of a versatile fluorinated c4. Enantioselective epoxidation of alkenes can also be accomplished using metal free. Myers sharpless asymmetric dihydroxylation reaction chem.
Pdf development of jacobsen asymmetric epoxidation and. Asymmetric dihydroxylation and aziridination of allenes. Dihydroxylation, aminohydroxylation and aziridination. Our synthesis of the cde ring fragment of pectenotoxin4 utilised two key steps to make the complex bicyclic ketal unit.
The reaction has been applied to alkenes of virtually. The sharpless asymmetric dihydroxylation was developed by k. The synthesis of enantiomerically pure 4,5disubstituted 2furanones is accomplished in three steps from aldehydes. Pdf novel synthesis of cp734432, an ep4 agonist, using. Wo1991016322a2 heterocyclic chiral ligands and method for. After our longrunning investigation of optimized methodology for the production of stereodefined diols based. To access a cheminform abstract of an article which was published elsewhere, please select a full. In the method of asymmetric dihydroxylation of the present invention, an olefin. Subsequent continuous efforts led to improve the reaction yield and enantioselectivity in the presence of osmiumcinchona alkaloid complexes scheme \\pageindex1\. The observed selectivities are rationalized in terms of electronic andor steric effects inherent to the substrate, superimposed on the substrates favorable or unfavorable interactions with the binding pocket of the ad ligand.
Asymmetric dihydroxylation and aziridination of allenes and related chemistry renmao liu brigham young university provo follow this and additional works at. Development of jacobsen asymmetric epoxidation and sharpless asymmetric dihydroxylation methods for the largescale preparation of a chiral dihydrobenzofuran epoxide. Multigramme synthesis and asymmetric dihydroxylation of a 4fluorobut2eenoate esters of crotonic acid were brominated on a multigramme scale using a free radical procedure. This process is experimental and the keywords may be updated as the learning algorithm improves. Asymmetric dihydroxylation an overview sciencedirect. Worlds best powerpoint templates crystalgraphics offers more powerpoint templates than anyone else in the world, with over 4 million to choose from.
Theyll give your presentations a professional, memorable appearance the kind of sophisticated look that todays audiences expect. However, in the asymmetric dihydroxylation nmo has not. A phase transfer catalysed fluorination transformed these species to the 4fluorobut2eenoates reproducibly and at. Asymmetric dihydroxylation of olefin using sba16supported chiral ligand 1. Liganddependent reversal of facial selectivity in the asymmetric. View the article pdf and any associated supplements and figures for a period of 48 hours. Article views are the countercompliant sum of full text article downloads since november 2008 both pdf and html across all institutions and individuals. Unlimited viewing of the articlechapter pdf and any associated. Asymmetric dihydroxylation of olefins using sharpless ligand in the presence of potassium osmate k 2 oso 2 oh 4 has been attained by recycling use of a catalytic amount of potassium ferricyanide k 3 fecn 6 in electrolysis media. Winner of the standing ovation award for best powerpoint templates from presentations magazine.
The asymmetric dihydroxylation procedure ad is applied to a variety of polyenes. Osmiumcatalyzed asymmetric dihydroxylation of olefins is an attractive method for. The reaction is performed in the presence of a chiral auxiliary. Remarkably high ee values in the asymmetric dihydroxylation reaction ad can be achieved with the pseudo. The catalytic asymmetric dihydroxylation ad discovered by sharpless, a nobel prize winner in 2001, has rapidly become an invaluable synthetic tool in the possibility of converting prochiral olefins to chiral vicinal diols. Preparation of mesoporous sba16 silicasupported biscinchona. A study in the correlation of the enol ether chain length and enantioselectivity. The dhq 2 aqn and dhqd 2 aqn ligands described by sharpless were the most effective. The reaction has been applied to alkenes of virtually every substitution, often high enantioselectivities are realized. Media in category sharpless asymmetric dihydroxylation the following 12 files are in this category, out of 12 total. Asymmetric synthesis of cyclic hydroxy ketones derived from enol ethers via sharpless asymmetric dihydroxylation. Relatively large volumes of organic extractant were necessary to isolate the highly watersoluble product, and chromatographic. Sharpless asymmetric dihydroxylation sharpless ad chem. Asymmetric dihydroxylation of alkenes can be modified to synthesize chiral amino alcohols, 429 in what is known as sharpless asymmetric aminohydroxylation or oxyamination.
The journal of organic chemistry 2003, 68 21, 80888091. Electronic helix theoryguided rational design of kinetic. Scalable synthesis of enantiomerically pure syn2,3dihydroxybutyrate by sharpless asymmetric dihydroxylation of pphenylbenzyl crotonate. Myers sharpless asymmetric dihydroxylation reaction chem 115. The prepared catalytic system provided 9093% yield of vicinal diol with 9299% enantioselectivity.
Molybdenumcatalyzed asymmetric anti dihydroxylation of. Ligands such as pyridine accelerate the osmylation of olefins criegee, r marchand, b. Percy1, giusepperinaudo1 andricardroig3,4 full research paper open access address. Rhodiumcatalysed vinyl 1,4conjugate addition coupled. Asymmetric dihydroxylation of olefins is a core transformation in organic chemistry and its synselective version is commonly catalysed by toxic osmium catalysts. Applications of sharpless asymmetric dihydroxylation in the total synthesis of natural products. Multigramme synthesis and asymmetric dihydroxylation of a 4fluorobut2eenoate jamesa. Free study guide jacobsen asymmetric epoxidation 20200410 sharpless epoxidation master organic chemistry epoxidation of alkenes with free study guide epoxidation of alkenes with free study guide epoxidation of alkenes with free study guide. All structured data from the file and property namespaces is available under the creative commons cc0 license. Other than for strictly personal use, it is not permitted to download or to.
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