- Ruthenium(II)-Catalyzed Hydroarylation of Maleimides Using Carboxylic Acids as a Traceless Directing Group
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An efficient Ru(II)-catalyzed hydroarylation of maleimides with ready-stock aryl carboxylic acids has been developed based on weak carboxylate-directed ortho-C-H alkylation and concomitant decarboxylation processes, fabricating 3-aryl succinimides, a recurrent scaffold in drug molecules, in high yields (up to 97%). The protocol features operational simplicity, avoids the need for precious metal additives/oxidants, and offers broad substrate scope with formal meta- and para-selectivities. It represents the first example of Ru(II)-catalyzed direct arylation of maleimides with unbiased benzoic acids.
- Mandal, Anup,Sahoo, Harekrishna,Dana, Suman,Baidya, Mahiuddin
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supporting information
p. 4138 - 4141
(2017/08/15)
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- Mild Decarboxylative C?H Alkylation: Computational Insights for Solvent-Robust Ruthenium(II) Domino Manifold
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Computational studies on decarboxylative C?H alkenylations provided key insights into the solvent-robust nature of C?H activation/decarboxylation domino reactions. These properties were exploited for ruthenium(II)-catalyzed C?H alkylations by a decarboxylative process with ample scope under copper-free and silver-free reaction conditions.
- Kumar, N. Y. Phani,Rogge, Torben,Yetra, Santhivardhana Reddy,Bechtoldt, Alexander,Clot, Eric,Ackermann, Lutz
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supporting information
p. 17449 - 17453
(2017/10/23)
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- Highly Enantioselective Synthesis of Chiral Succinimides via Rh/Bisphosphine-Thiourea-Catalyzed Asymmetric Hydrogenation
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We have successfully developed a highly enantioselective hydrogenation of various 3-aryl and 3-methyl maleinimides to access enantiomerically pure 3-substituted succinimides catalyzed by Rh/bisphosphine-thiourea (ZhaoPhos). This efficient catalytic system furnished the desired 3-substituted succinimide products with high yields and enantioselectivities (up to 99% yield, full conversions, almost all 3-aryl succinimide products up to 99% ee, and 3-methyl succinimide with 83% ee). Our catalytic system has a strong substrate tolerance and generality. Whether the N-substituted group of maleinimides is H or other protecting groups, the maleinimides were hydrogenated well (up to >99% ee, 99% yield). Moreover, the hydrogenation succinimide products can be readily utilized for the construction of biologically active molecules, such as chiral amides and pyrrolidines.
- Han, Zhengyu,Li, Pan,Zhang, Zongpeng,Chen, Caiyou,Wang, Qian,Dong, Xiu-Qin,Zhang, Xumu
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p. 6214 - 6218
(2016/09/09)
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- Base-Free Conditions for Rhodium-Catalyzed Asymmetric Arylation to Produce Stereochemically Labile α-Aryl Ketones
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The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was found to be efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer, [{RhCl((R)-diene?)}2], in the absence of bases in toluene/H2O to give 2,2-dialkyl 4-aryl cyclopentane-1,3-diones in high yields with high enantioselectivity. Such compounds can not be obtained with high enantiomeric purity under the standard basic conditions used for rhodium-catalyzed asymmetric arylation because the α-aryl ketone products undergo racemization under the basic conditions. Forget about bases, score a home run: The asymmetric arylation of 2,2-dialkyl cyclopent-4-ene-1,3-diones with aryl boronic acids was efficiently catalyzed by a chiral diene-rhodium μ-chloro dimer without a base in toluene/H2O (see scheme). The resulting α-aryl ketones can not be obtained with high ee values under the standard basic conditions for rhodium-catalyzed asymmetric arylation owing to their racemization in the presence of a base.
- Dou, Xiaowei,Lu, Yixin,Hayashi, Tamio
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supporting information
p. 6739 - 6743
(2016/06/09)
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- Direct Synthesis of Chiral 3-Arylsuccinimides by Rhodium-Catalyzed Enantioselective Conjugate Addition of Arylboronic Acids to Maleimides
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Chiral rhodium catalysts comprising 2,5-diaryl- substituted bicyclo[2.2.1]diene ligands L1-L10 were utilized in the enantioselective 1,4-addition reaction of arylboronic acids to N-substituted maleimides. In the presence of 2.5mol % of RhI/L2, enantioenriched conjugate addition adducts were isolated in 72-99 % yields with 86-98 %ee. This protocol offers a convenient method to access a variety of 3-arylsuccinimides in a highly enantioselective manner. Maleimides with readily cleavable N-protecting groups were tolerated enabling the synthesis of useful synthetic intermediates. Pyrrolidine 4, a biologically active compound, and pyrrolidine 5, an ent-precursor to an HSD-1 inhibitor, were synthesized to demonstrate the utility of this method. The road to rhodium! Enantioselective conjugate addition of a range of arylboronic acids to variously N-substituted maleimides, catalyzed by RhI complexes prepared in situ using chiral bicyclo[2.2.1]diene ligands, afforded the corresponding 3-arylsuccinimides with up to 98 %ee at 50 C (see scheme).
- Gopula, Balraj,Yang, Shu-Han,Kuo, Ting-Shen,Hsieh, Jen-Chieh,Wu, Ping-Yu,Henschke, Julian P.,Wu, Hsyueh-Liang
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supporting information
p. 11050 - 11055
(2015/11/10)
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- Phosphine-olefin ligands based on a planar-chiral (π-Arene)chromium scaffold: Design, synthesis, and application in asymmetric catalysis
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The NMR and X-ray crystallographic studies clarified that planar-chiral alkenylene-bridged (phosphino-π-arene)(phosphine)chromium complexes 3 were capable of coordinating to a rhodium(I) cation in a bidentate fashion at the (π-arene)-bound phosphorus atom
- Ogasawara, Masamichi,Tseng, Ya-Yi,Arae, Sachie,Morita, Tomotaka,Nakaya, Takeshi,Wu, Wei-Yi,Takahashi, Tamotsu,Kamikawa, Ken
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supporting information
p. 9377 - 9384
(2014/07/21)
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- Low-temperature Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds
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Rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds was achieved at temperatures below 0 C using a Rh/MeO-F12-BIPHEP catalyst. The reaction of cyclohexenone or N-R-maleimide with arylboronic acids proceeded even at -80 C in the presence of the Rh catalyst. In the latter case, high enantioselectivity was observed because a low-temperature method was used, regardless of the type of substituent on maleimide.
- Korenaga, Toshinobu,Ko, Aram,Shimada, Kazuaki
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p. 9975 - 9980
(2013/10/22)
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- Tropanes as scaffolds for phosphorus-olefin ligands and their application in asymmetric catalysis
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Tropane-derived phosphorus-olefin hybrid ligands bearing various combinations of P-units (chiral BINOL-derived units/achiral PPh 2-units) with a tropene skeleton (chiral/achiral) have been synthesized and used in Cu-catalysed conjugate 1,4-addi
- Vlahovic, Sandra,Schaedel, Nicole,Tussetschlaeger, Stefan,Laschat, Sabine
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supporting information
p. 1580 - 1590
(2013/04/23)
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- Room-temperature Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to maleimides and enones in the presence of CF3-substituted MeOBIPHEP analogues
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A Rh-based catalytic system implying electron-poor MeOBIPHEP analogues has been developed for the 1,4-addition of boronic acids to maleimides and enones under mild conditions at room temperature and led to succinimide derivatives and arylated cyclic ketones in good to excellent yields and ee. We uncovered the crucial role of the electronic and steric properties of diphosphine ligand and observed a strong boronic acid/ligand dependency in the case of maleimide derivatives and substrate/ligand matching in the case of cyclic enones.
- Le Boucher D'Herouville, Florent,Millet, Anthony,Scalone, Michelangelo,Michelet, Veronique
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experimental part
p. 6925 - 6930
(2011/10/08)
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- Sulfoxide-alkene hybrids: A new class of chiral ligands for the Hayashi-Miyaura reaction
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Sulfoxide-alkene hybrids are introduced as a new class of chiral heterodentate ligands for the Hayashi-Miyaura reaction. The synthesis of these ligands was achieved without the use of protecting groups. A chiral resolution was performed via simple column-chromatographic separation of the diastereomeric ligands. Both diastereomers proved to be excellent ligands in Rh-catalyzed 1,4-addition reactions, furnishing chiral products with high enantioselectivities and, remarkably, opposite stereoconfigurations.
- Thaler, Tobias,Guo, Li-Na,Steib, Andreas K.,Raducan, Mihai,Karaghiosoff, Konstantin,Mayer, Peter,Knochel, Paul
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supporting information; experimental part
p. 3182 - 3185
(2011/08/06)
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- Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated ketones with DIFLUORPHOS and SYNPHOS analogues
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Applications of electron-deficient DIFLUORPHOS and SYNPHOS analogues in the rhodium-catalyzed asymmetric conjugate addition of boronic acids to α,β-unsaturated ketones afford the 1,4-addition adducts in yields up to 92% and with 99% ee. Particularly, a Rh-catalyzed asymmetric 1,4-addition of arylboronic acids to nonsubstituted maleimide substrates using the (R)-3,5-diCF3-SYNPHOS ligand is also reported. This protocol provides access to various enantioenriched 3-substituted succinimide units of biological interest, in high yields and good to excellent ee up to 93%, which could be upgraded up to 99% ee, after a single crystallization.
- Berhal, Farouk,Wu, Zi,Genet, Jean-Pierre,Ayad, Tahar,Ratovelomanana-Vidal, Virginie
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scheme or table
p. 6320 - 6326
(2011/10/05)
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- [5]Ferrocenophanene-Phosphane Ligands for Enantioselective Rh-Catalyzed Conjugate Additions
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Ferrocenophanene-phosphane ligands with bridged cyclopentadienyl rings have been synthesized and characterized by spectroscopic methods. Rhodium complexes of these ligands can catalyze the Michael addition of phenylboronic acid to cyclic enones and lacton
- Csizmadiova, Jana,Meciarova, Maria,Rakovsky, Erik,Horvath, Branislav,sebesta, Radovan
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experimental part
p. 6110 - 6116
(2011/12/03)
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- Chemoenzymatic synthesis and application of bicyclo [2.2.2] octadiene ligands: Increased efficiency in rhodium-catalyzed asymmetric conjugate additions by electronic tuning
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(Figure Presented) On your bi(cycle)kel A series of 1,4dimethyl bicyclic [2.2.2] diene ligands with tunable substitution at the bridge positions was accessed using a lipase resolution and a high yielding six step sequence (see scheme). The bridgehead meth
- Luo, Yunfei,Cornell, Andrew J.
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supporting information; experimental part
p. 2750 - 2754
(2010/07/03)
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- Palladium-catalyzed selective alkoxycarbonylation of α,β-unsaturated amides: a novel approach toward new ω-amido esters and N-substituted cyclic succinimides
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The alkoxycarbonylation of α,β-unsaturated amides proceeded efficiently and regioselectivity to give ω-amido esters with complete conversion in the presence of the catalyst system: Pd(PPh3)2Cl2/MeOH/CO/H2O. The reaction was successfully applied to the alkoxycarbonylation of bis-acrylamides yielding, selectively, the corresponding di-ω-amido esters. These mono and di-ω-amido esters have been used as precursors for the synthesis of N-substituted cyclic succinimides in moderate to high yields.
- Suleiman, Rami,El Ali, Bassam
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scheme or table
p. 3211 - 3215
(2010/08/19)
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- Kinetic resolution of racemic pyrrolidine-2,5-diones using chiral oxazaborolidine catalysts
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Kinetic resolution of racemic C-3 substituted pyrrolidine-2,5-diones has been achieved for the first time using highly efficient oxazaborolidine catalysts derived from cis-1-amino-indan-2-ol. The Royal Society of Chemistry.
- Barker, Mike D.,Dixon, Rachel A.,Jones, Simon,Marsh, Barrie J.
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p. 2218 - 2220
(2008/12/22)
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- Chiral phosphine-olefin ligands in the rhodium-catalyzed asymmetric 1,4-addition reactions
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A full overview on the use of chiral phosphine-olefin ligands 1 in the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to α,β-unsaturated carbonyl compounds is described. Effective chiral environment of a Rh/1 complex was shown to resemble that of a Rh/(R,R)-Ph-bod* complex by comparing the experimental results as well as the X-ray crystal structures. High catalytic activity of a Rh/1 complex was disclosed and the catalytic cycle involving a trimer-monomer equilibrium was established through mechanistic studies using a reaction calorimeter and 31P NMR spectroscopy. A negative nonlinear effect derived from an inactive trimer-active monomer equilibrium of the catalyst was also successfully observed.
- Duan, Wei-Liang,Iwamura, Hiroshi,Shintani, Ryo,Hayashi, Tamio
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p. 2130 - 2138
(2007/10/03)
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- Transition metal catalysts
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The present invention relates to stereoisomerically enriched phosphorus compounds, transition metal catalysts which can be prepared therefrom and their use in stereoselective catalytic processes, and also a process for preparing the stereoisomerically enr
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Page/Page column 6
(2010/11/27)
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- Chiral phosphane alkenes (PALs): Simple synthesis, applications in catalysis, and functional hemilability
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A simple synthesis of a chiral phosphane alkene (PAL) involves: 1) palladium-catalyzed Suzuki coupling of 10-bromo-5H-dibenzo[a,d]cyclohepten-5-ol (1) with phenylboronic acid to give quantitatively 10-phenyl-5H-dibenzo[a,d] cyclohepten-5-ol (2); 2) reacti
- Piras, Elisabetta,Laeng, Florian,Rueegger, Heinz,Stein, Daniel,Woerle, Michael,Gruetzmacher, Hansjoerg
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p. 5849 - 5858
(2008/03/11)
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- FUSED BENZENE DERIVATIVE AND USE
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The present invention provides a compound represented by the general formula: [wherein Ring A represents an optionally substituted 5- to 8-membered ring, Ring B represents a further optionally substituted 4- to 10-membered ring, Ring C represents a further optionally substituted benzene ring, X1 represents carbon atom, X2 represents a carbon atom, an oxygen atom, etc., W represents a nitrogen atom, etc., Y11 represents a group represented by the formula CR2R3' (wherein R2 represents a hydrogen atom, a cyano group, a nitro group, etc., and R3' represents a hydrogen atom, a cyano group, a nitro group, etc., respectively), Y21 represents a group represented by the formula CR4R5' (wherein R4 represents a hydrogen atom, a cyano group, a nitro group, etc., and R5' represents a hydrogen atom, a cyano group, a nitro group, etc., respectively), etc., and R1 represents an electron-withdrawing group, respectively. The formula represents a single bond or a double bond] or a salt thereof, which is useful as an androgen receptor modulator.
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Page/Page column 56
(2010/02/12)
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- Chiral phosphine-olefin bidentate ligands in asymmetric catalysis: Rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to maleimides
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(Chemical Equation Presented) Two is better than one: Novel chiral phosphine - olefin ligands 1 a and 1 b act as bidentate ligands with some transition metals and have proved to be highly effective in the rhodium-catalyzed asymmetric 1,4-addition of aryl boronic acids to maleimides with high enantio-selectivity (see scheme).
- Shintani, Ryo,Duan, Wei-Liang,Nagano, Takashi,Okada, Atsushi,Hayashi, Tamio
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p. 4611 - 4614
(2007/10/03)
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- Chiral norbornadienes as efficient ligands for the rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds
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(Chemical Equation Presented) A rhodium-catalyzed asymmetric 1,4-addition of arylboronic acids to fumaric and maleic compounds has been developed. While phosphorus-based chiral ligands fail to induce high stereoselectivity, chiral norbornadiene ligands have proved to be uniquely effective to achieve high enantioselectivity in these 1,4-addition reactions.
- Shintani, Ryo,Ueyama, Kazuhito,Yamada, Ichiro,Hayashi, Tamio
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p. 3425 - 3427
(2007/10/03)
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