- Enantioselective Allylation of Alkenyl Boronates Promotes a 1,2-Metalate Rearrangement with 1,3-Diastereocontrol
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Alkenyl boronates add to Ir(π-allyl) intermediates with high enantioselectivity. A 1,2-metalate shift forms a second C-C bond and sets a 1,3-stereochemical relationship. The three-component coupling provides tertiary boronic esters that can undergo multiple additional functionalizations. An extension to trisubstituted olefins sets three contiguous stereocenters.
- Davis, Colton R.,Luvaga, Irungu K.,Ready, Joseph M.
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supporting information
p. 4921 - 4927
(2021/05/04)
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- Method for synthesizing chiral phosphite ligand based on R - 2 - phenylethylamine
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The invention discloses a method for synthesizing chiral phosphite ligand based on R - 2 -phenylethylamine. To the method, R - 2 -phenylethylamine is reacted with acetophenone to obtain the imine intermediate, and then is mixed with H. 2 Under
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- Development of Axially Chiral Cyclo-Biaryldiol Ligands with Adjustable Dihedral Angles
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A new type of axially chiral cyclo-[1,1′-biphenyl]-2,2′-diol (CYCNOL) ligands with adjustable dihedral angles have been developed by varying the bridge chain length. Eight-, nine- and ten-membered cyclo-ligands were prepared and evaluated by using two representative examples: enantioselective additions of diethylzinc to aldehydes and organometallic reagents to enones. The results revealed that the fine regulation of dihedral angles through variation of the bridge chain length was effective in the asymmetric synthesis.
- Zhang, Pengxiang,Yu, Jipan,Peng, Fei,Wu, Xudong,Jie, Jiyang,Liu, Can,Tian, Hua,Yang, Haijun,Fu, Hua
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supporting information
p. 17477 - 17484
(2016/11/23)
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- Rapid identification of a scalable catalyst for the asymmetric hydrogenation of a sterically demanding aryl enamide
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High throughput screening was used to find a cost-effective and scalable catalyst for the asymmetric hydrogenation of a sterically demanding enamide as an intermediate towards a new potent melanocortin receptor agonist useful in the treatment of obesity.
- Lefort, Laurent,Boogers, Jeroen A. F.,Kuilman, Thijs,Vijn, Robert Jan,Janssen, John,Straatman, Harrie,De Vries, Johannes G.,De Vries, Andre H. M.
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supporting information; experimental part
p. 568 - 573
(2011/07/08)
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- Efficient, selective, and green: Catalyst tuning for highly enatioselective reactions of ethylene
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Fine tuning of the biaryl and amino moieties of Feringa's phosphoramidite ligands yields structurally simpler, yet more efficient and selective, ligands for asymmetric hydrovinylation of vinylarenes and acylic 1,3-dienes. The enantioselectivities and yields observed in the formation of the 3-arylbutenes are among the highest for all asymmetric catalytic processes reported to date for the synthesis of intermediates for the widely used antiinflammatory 2-arylpropionic acids including naproxen, ibuprofen, fenoprofen, and flurbiprofen.
- Smith, Craig R.,Rajanbabu
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supporting information; experimental part
p. 1657 - 1659
(2009/04/10)
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- Novel Compounds 679
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The invention provides compounds of formula (I), processes for their preparation, pharmaceutical compositions containing them, a process for preparing the pharmaceutical compositions, and their use in therapy, wherein R1, R2, R3
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Page/Page column 12
(2008/12/08)
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- The development of an asymmetric Nicholas reaction using chiral phosphoramidite ligands
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An asymmetric version of the Nicholas reaction involving the use of chiral phosphoramidite ligands has been developed. Treatment of a cobalt carbonyl complexed propargylic alcohol with two equivalents of the chiral ligand, followed by reaction with a sily
- Ljungdahl, Natalie,Pera, Núria Parera,Andersson, Kristian H. O.,Kann, Nina
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p. 394 - 398
(2008/09/17)
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- Copper-catalyzed asymmetric conjugate addition of trialkylaluminium reagents to trisubstituted enones: Construction of chiral quaternary centers
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Me3Al, Et1Al, and vinylalane species undergo enantioselective conjugate addition to a wide range of 2- or 3-substituted enones (cyclopent-2enones, cyclohex-2-enones, 3-methyl cyclohept-2-enone) in the presence of catalytic amount of copper salt (copper thiophene carboxylate, [Cu(CH3-CN)4]BF4 or [CuOTf]2· C6H6) and tropos-phosphoramidite-based ligand. Thus, chiral quaternary centers can be built, with up to 98% ee after rigorous optimization of experimental conditions. It was shown that the main important parameter was the order of the introduction of the reagents. Then, the generated enantioenriched aluminium enolates and the chiral conjugate adducts were functionalized and used for subsequent reactions.
- Vuagnoux-D'Augustin, Magali,Alexakis, Alexandre
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p. 9647 - 9662
(2008/12/21)
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- Enantioselective copper-catalyzed conjugate addition to trisubstituted cyclohexenones: Construction of stereogenic quaternary centers
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Trimethyl- and triethylaluminum undergo enantioselective conjugate addition to 3-and 2-substituted cyclohexenones in the presence of catalytic amounts of a Cu salt and a phosphoramidite ligand L* (see scheme). Thus, chiral quaternary centers can be built with up to 96.6% ee. Functionalized enones lead to bicyclic structures by a subsequent aldol reaction.
- D'Augustin, Magali,Palais, Laeticia,Alexakis, Alexandre
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p. 1376 - 1378
(2007/10/03)
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- ENANTIOSELECTIVE AMINATION AND ETHERIFICATION___________________
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The present invention is directed to a catalyst composition, comprising: (1) a catalyst precursor having the general structure MSXn wherein M is a transition metal selected from the group consisting of iridium, molybdenum, and tungsten; S is a coordinating ligand; X is a counterion; and n is an integer from 0 to 5; and (2) a phosphoramidite ligand having the structure wherein O-Cn-O is an aliphatic or aromatic diolate and wherein R1, R2, R3 and R4 are selected from the group consisting of substituted or unsubstituted aryl groups, substituted or unsubstituted heteroaryl groups, substituted or unsubstituted aliphatic groups, and combinations thereof, with the proviso that at least one of R1, R2, R3, or R4 must be a substituted or unsubstituted aryl or heteroaryl group. The present invention is also directed to activated catalysts made from the above catalyst composition, as well as methods of allylic amination and etherification using the above catalysts.
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- Conjugate Addition of Organozinc Compounds to Nitroolefins
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Symmetrical (R2Zn) or mixed diorganozinc compounds (R 1ZnR2) smoothly react with a series of nitroolefins in the presence of catalytic amounts of copper(I) salts and provide synthetically versatile nitro compounds in moderate to good yields. Simple alkyl groups, functionalized residues, or mixed trimethylsilylmethyl organozinc compounds (TMSM)ZnR may be employed for conjugate addition, while the TMSM group is not being transferred. ipso-Substitution is observed in absence of the copper(I) salt. Enantiomerically pure copper(I) complexes with BINOL based chiral phosphoramidite ligands efficiently catalyze the addition of dialkylzinc compounds to nitroalkenes. For instance, diethylzinc addition occurs with high yields and excellent enantioselectivity. Nitrostyrene, 3-nitroacrolein dimethylacetal, and 3-nitroacrylates have been used as substrates. The nitroolefin moiety predominates over the acrylate moiety and acts as the more powerful Michael acceptor. 2-Alkyl-3-nitropropanoates are exclusively obtained with excellent yield and enantioselectivity. The products can easily be transformed into β2-homoamino acids, compounds of high relevance for different areas of preparative organic chemistry.
- Rimkus, Audrius,Sewald, Norbert
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p. 135 - 146
(2007/10/03)
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- First synthesis of a beta(2)-homoamino acid by enantioselective catalysis.
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The enantioselective conjugate addition of diethylzinc to the activated nitroolefin methyl 3-nitropropenoate is efficiently catalyzed by copper(I) complexes with BINOL-based enantiopure phosphoramidite ligands. The nitroolefin moiety acts as the predomina
- Rimkus, Audrius,Sewald, Norbert
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- Enantioselective catalytic conjugate addition of dialkylzinc reagents using copper-phosphoramidite complexes; ligand variation and non-linear effects
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A variety of new chiral phosphoramidites was synthesised and tested in the copper-catalysed enantioselective conjugate addition of diethylzinc to cyclohexenone and chalcone in order to assess the structural features that are important for stereocontrol. A
- Arnold, Leggy A.,Imbos, Rosalinde,Mandoli, Alessandro,De Vries, André H.M.,Naasz, Robert,Feringa, Ben L.
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p. 2865 - 2878
(2007/10/03)
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