- Ni(0)-Catalyzed Three-Component Coupling Reaction of Tetrafluoroethylene and N-Sulfonyl-Substituted Imines with Silanes via Aza-Nickelacycles
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A nickel-catalyzed three-component coupling reaction of tetrafluoroethylene (TFE) and N-sulfonyl-substituted imines with silanes that furnishes a variety of fluorine-containing amines is disclosed. Stoichiometric experiments revealed that the aza-nickelac
- Shirataki, Hiroshi,Ono, Takafumi,Ohashi, Masato,Ogoshi, Sensuke
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supporting information
p. 851 - 856
(2019/05/16)
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- Enantioselective Mannich Reaction of Glycine Iminoesters with N-Phosphinoyl Imines: A Bifunctional Approach
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A bifunctional catalytic approach for the asymmetric Mannich reaction of glycine iminoesters with N-phosphinoyl imines has been developed. By the combination of metal catalysis and organocatalysis, the vicinal two stereogenic centers were efficiently constructed, affording a wide range of syn-diamino esters in high yields with excellent enantio- and diastereoselectivities (up to >99:1 dr, 99% ee).
- Zhang, Changhui,Yang, Jiao,Zhou, Wenqiang,Tan, Qiuyuan,Yang, Zhao,He, Ling,Zhang, Min
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supporting information
p. 8620 - 8624
(2019/11/03)
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- Enantioselective Synthesis of anti-1,2-Diamines by Cu-Catalyzed Reductive Couplings of Azadienes with Aldimines and Ketimines
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Here we report highly efficient and chemoselective azadiene-imine reductive couplings catalyzed by (Ph-BPE)Cu-H that afford anti-1,2-diamines. In all cases, reactions take place with either aldimine or ketimine electrophiles to deliver a single diastereom
- Shao, Xinxin,Li, Kangnan,Malcolmson, Steven J.
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supporting information
p. 7083 - 7087
(2018/05/29)
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- Single or Synergistic Kinetic Resolutions of Chiral Allylalanes: Two Complementary Routes for the Asymmetric Synthesis of Syn Homoallylamines
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Two strategies based on kinetic resolution(s) of chiral alanes and providing enantioenriched syn homoallylamines are reported. The first implies a single kinetic resolution of the alane using camphor; the second requires two sequential kinetic resolutions using the synergistic combination of (-)-camphor/(R)-tert-butylsulfinamide-derived imines. This syn selectivity, specific to the use of allyaluminum, opens the way to the preparation of valuable building blocks as illustrated by the synthesis of (+)-epilupinamine.
- Coffinet, Micha?l,Behr, Jean-Bernard,Jaroschik, Florian,Harakat, Dominique,Vasse, Jean-Luc
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supporting information
p. 6728 - 6731
(2017/12/26)
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- Iron-Catalyzed Asymmetric Nitro-Mannich Reaction
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The first enantioselective addition of nitroalkanes to imines (nitro-Mannich reaction), mediated by an iron(II) catalyst assembled by a hindered hydroxyethyl-pybox ligand, is described. This valuable carbon-carbon bond-forming reaction proceeds smoothly at room temperature to afford enantioenriched β-nitro amines in good yields and high enantioselectivity, up to 98% with unprecedentedly low iron catalyst loading (5 mol %).
- Dudek, Agata,Mlynarski, Jacek
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p. 11218 - 11224
(2017/10/27)
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- Highly Diastereo- and Enantioselective Cu-Catalyzed Borylative Coupling of 1,3-Dienes and Aldimines
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A Cu-catalyzed diastereo- and enantioselective borylative coupling reaction of 1,3-dienes with imines was realized. Branched homoallylic amines are readily prepared in a syn-selective manner with high regio-, diastereo- and enantioselectivity. Moreover, t
- Jiang, Liyin,Cao, Peng,Wang, Min,Chen, Bin,Wang, Bing,Liao, Jian
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supporting information
p. 13854 - 13858
(2016/10/26)
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- (Thiolan-2-yl)diphenylmethyl benzyl ether/N,N′-diarylurea cocatalyzed asymmetric aziridination of cinnamyl bromide and aryl aldimine
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A dual catalyst system using THT-based chiral sulfide 2a and H-bond donor 10a was developed for the asymmetric imino Corey-Chaykovsky reaction. Under the optimum reaction conditions, cinnamyl bromide reacted with a wide scope of N-diphenylphosphinic aldim
- Wang, Shang-Hua,Chein, Rong-Jie
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supporting information
p. 2607 - 2615
(2016/05/11)
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- Nitroxyl-Radical-Catalyzed Oxidative Coupling of Amides with Silylated Nucleophiles through N-Halogenation
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A nitroxyl-radical-catalyzed oxidative coupling reaction between amines with an N-protecting electron-withdrawing group (EWG) and silylated nucleophiles was developed to furnish coupling products in high yields, thus opening up new frontiers in organocatalyzed reactions. This reaction proceeded through the activation of N-halogenated amides by a nitroxyl-radical catalyst, followed by carbon–carbon coupling with silylated nucleophiles. Studies of the reaction mechanism indicated that the nitroxyl radical activates N-halogenated amides, which are generated from N-EWG-protected amides and a halogenation reagent, to give the corresponding imines.
- Moriyama, Katsuhiko,Kuramochi, Masako,Fujii, Kozo,Morita, Tsuyoshi,Togo, Hideo
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supporting information
p. 14546 - 14551
(2016/11/23)
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- Nucleophilic addition of TMSCCl3 to N-phosphinoyl benzaldimines: A route to N-phosphinoyl-α-(trichloromethyl)benzylamines
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Nucleophilic addition of readily available TMSCCl3 to N-phosphinoyl benzaldimines allows preparation of N-phosphinoyl-α-(trichloromethyl)benzylamines. Typically, the reaction in THF at room temperature using tetrabutylammonium difluorotriphenylsilicate (TBAT) as a catalytic promoter, afforded very good yields (65-95% range) for most derivatives within 1 h at room temperature.
- Wahl, Benoit,Cabré, Albert,Woodward, Simon,Lewis, William
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supporting information
p. 5829 - 5831
(2015/02/02)
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- A general aminocatalytic method for the synthesis of aldimines
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A general and efficient biomimetic method for the synthesis of aldimines from aldehydes and compounds bearing the NH2 group in the presence of pyrrolidine as a catalyst has been developed. These organocatalytic reactions, based on the application of the concept of nucleophilic catalysis, proceed with outstanding yields in the absence of acids and metals under simple conditions and minimum experimental manipulation. The method has been mainly applied to the synthesis of N-sulfinyl and N-sulfonyl imines, but its general validity has been proven with the preparation of representative N-phosphinoyl, N-alkyl, and N-aryl imines. These unprecedented reactions, which presumably occur via iminium activation without requiring acidic conditions, are an interesting and competitive alternative to the classical methods for preparing aldimines.
- Morales, Sara,Guijarro, Fernando G.,Garcia Ruano, Jose Luis,Cid, M. Belen
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supporting information
p. 1082 - 1089
(2014/02/14)
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- A new reactivity mode for the diazo group: Diastereoselective 1,3-aminoalkylation reaction of β-amino-α-diazoesters to give triazolines
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A novel mode of reactivity for the diazo group, the 1,3-addition of a nucleophile and an electrophile to the diazo group, has been realized in the intramolecular aminoalkylation of β-amino-α-diazoesters to form tetrasubstituted 1,2,3-triazolines. The reaction exhibited a broad scope, good functional group tolerance, and excellent diastereoselectivity. In addition, a new Au-catalyzed intramolecular transannulation reaction of the obtained propargyl triazolines to give pyrroles has been discovered.
- Kuznetsov, Alexey,Gulevich, Anton V.,Wink, Donald J.,Gevorgyan, Vladimir
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supporting information
p. 9021 - 9025
(2014/09/29)
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- Enantioselective synthesis of diaryl aziridines using tetrahydrothiophene- based chiral sulfides as organocatalysts
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This work describes catalytic and asymmetric aziridinations (15 examples, 95-98% ee) of benzyl bromide and imines via the imino Corey-Chaykovsky reaction using (thiolan-2-yl)diarylmethanol benzyl ether as an organocatalyst. The catalyst and analogues thereof were prepared through an expeditious and efficient synthetic route featuring a double nucleophilic substitution and Shi epoxidation as key steps.
- Huang, Meng-Ting,Wu, Hsin-Yi,Chein, Rong-Jie
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supporting information
p. 1101 - 1103
(2014/01/17)
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- Organocatalytic trifluoromethylation of imines using phase-transfer catalysis with phenoxides. A general platform for catalytic additions of organosilanes to imines
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A new approach to additions of silicon nucleophiles to imines was developed. The method is based on the phase-transfer of phenoxides by ammonium catalysts, overcoming the inability of amide adducts in promoting the reactions.
- Bernardi, Luca,Indrigo, Eugenio,Pollicino, Salvatore,Ricci, Alfredo
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supporting information; experimental part
p. 1428 - 1430
(2012/03/11)
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- Activation of the Si-B Linkage: Copper-Catalyzed addition of nucleophilic silicon to imines
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Activation of the Si-B bond through copper-catalyzed transmetalation quickly developed into a practical method to generate Cu-Si reagents These silicon nucleophiles cleanly add to aldehyde-derived imine electrophiles to form R-silylated amines in protic media, and no carbon-tonitrogen Brook-type rearrangement of the intermediate anion is observed. Aside from electron-withdrawing groups at the imine nitrogen atom, for example, SO2Tol and P(O)Ph2, previously delicate nitrogen substituents such as phenyl or benzhydryl are tolerated. The same protocol also allows the unprecedented addition to representative ketone-derived imines.
- Vyas, Devendra J.,Froehlich, Roland,Oestreich, Martin
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supporting information; experimental part
p. 2094 - 2097
(2011/06/22)
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- Enantioselective synthesis of homoallylic amines through reactions of (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkene-substituted aldimines catalyzed by chiral C 1-symmetric NHC-Cu complexes
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A catalytic method for enantioselective synthesis of homoallylamides through Cu-catalyzed reactions of stable and easily accessible (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkenyl-substituted N-phosphinoylimines is disclosed. Transformations are promoted by 1-5 mol % of readily accessible NHC-Cu complexes, derived from C1-symmetric imidazolinium salts, which can be prepared in multigram quantities in four steps from commercially available materials. Allyl additions deliver the desired products in up to quantitative yield and 98.5:1.5 enantiomeric ratio and are amenable to gram-scale operations. A mechanistic model accounting for the observed selectivity levels and trends is proposed.
- Vieira, Erika M.,Snapper, Marc L.,Hoveyda, Amir H.
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supporting information; experimental part
p. 3332 - 3335
(2011/05/04)
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- Quantification of the electrophilic reactivities of aldehydes, imines, and enones
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The rates of the epoxidation reactions of aldehydes, of the aziridination reactions of aldimines, and of the cyclopropanation reactions of α,β-unsaturated ketones with aryl-stabilized dimethylsulfonium ylides have been determined photometrically in dimethyl sulfoxide (DMSO). All of these sulfur ylide-mediated cyclization reactions as well as the addition reactions of stabilized carbanions to N-tosyl-activated aldimines have been shown to follow a second-order rate law, where the rate constants reflect the (initial) CC bond formation between nucleophile and electrophile. The derived second-order rate constants (log k2) have been combined with the known nucleophilicity parameters (N, sN) of the aryl-stabilized sulfur ylides 4a,b and of the acceptor-substituted carbanions 4c-h to calculate the electrophilicity parameters E of aromatic and aliphatic aldehydes (1a-i), N-acceptor-substituted aromatic aldimines (2a-e), and α,β-unsaturated ketones (3a-f) according to the linear free-energy relationship log k 2 = sN(N + E) as defined in J. Am. Chem. Soc.2001, 123, 9500-9512. The data reported in this work provide the first quantitative comparison of the electrophilic reactivities of aldehydes, imines, and simple Michael acceptors in DMSO with carbocations and cationic metal-π complexes within our comprehensive electrophilicity scale.
- Appel, Roland,Mayr, Herbert
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body text
p. 8240 - 8251
(2011/07/29)
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- Aromatic motifs in the design of Ephedra ligands for application in the asymmetric addition of diethylzinc to aldehydes and diphenylphosphinoylimines
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Using N-benzylephedrine as a model, a collection of N-arylmethylephedrine derivatives has been prepared. These derivatives were prepared by treatment of ephedrine with selected aldehydes to create oxazolidines 8a-e. Reduction of the oxazolidines with lith
- Banerjee, Sucharita,Camodeca, Anthony J.,Griffin, Gregory G.,Hamaker, Christopher G.,Hitchcock, Shawn R.
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scheme or table
p. 549 - 557
(2010/10/02)
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- N-Pyridylmethylephedrine derivatives in the catalytic asymmetric addition of diethylzinc to aldehydes and diphenylphosphinoylimines
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N-Pyridylmethyl-substituted Ephedra derivatives were synthesized by either direct alkylation or reductive alkylation of (1R,2S)-norephedrine, (1S,2S)-pseudo norephedrine, and (1R,2S)-ephedrine. These derivatives were then employed in asymmetric addition reactions with diethylzinc and aldehydes and diphenylphosphinoylimines. The use of the diastereomers from the Ephedra family allowed for a systematic evaluation of the contribution of the N-pyridylmethyl.
- Banerjee, Sucharita,Groeper, Jonathan A.,Standard, Jean M.,Hitchcock, Shawn R.
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experimental part
p. 2154 - 2161
(2010/03/03)
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- Enantioselective binaphthophosphepine-promoted [3+2] annulations of N-Ts- and N-DPP-imines with allenoates and 2-butynoates
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The use of binaphthophosphepine 1a as a catalyst for the [3+2] cyclisation between allenoates or 2-butynoates and imines was investigated. The effects of the imine protecting group on both the catalytic activity and enantioselectivity were determined by c
- Pinto, Nathalie,Fleury-Bregeot, Nicolas,Marinetti, Angela
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body text
p. 146 - 151
(2009/07/05)
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- Reaction prospecting by 31P NMR: enantioselective rhodium-DuPhos catalysed addition of ZnMe2 to diphenylphosphinoylimines
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Chiral shift 31P NMR spectroscopy allows the identification of ligand leads in asymmetric catalyst systems for ZnMe2 addition to ArCH{double bond, long}NP(O)Ph2. Subsequent GC-based optimisation shows [RhCl(CH2{double bond, long}CH2)2]2 and (R,R)-MeDuPhos to be the optimal pre-catalyst combination (product in 78-93% ee). Transmetallation of [(MeDuPhos)Rh{N(P(O)Ph2-CHMeAr}] with ZnMe2 appears to be the rate limiting step of the catalytic cycle as competing coordination by the imine starting material leads to Ph2P(O)NHCH2Ar via MVP hydrogen-transfer. This limitation can largely be overcome by the slow addition of the imine.
- Crampton, Rosemary H.,Hajjaji, Samir El,Fox, Martin E.,Woodward, Simon
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experimental part
p. 2497 - 2503
(2010/04/05)
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- Enantioselective Strecker-type reaction of phosphinoyl ketimines catalyzed by a chiral Zr-bipyridyldiol catalyst
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An enantioselective Strecker reaction of N-diphenylphosphinoyl ketimines with TMSCN employing a chiral zirconium complex formed from chiral bipyridyl diol 1 as catalyst is described. The catalytic efficiency of chiral ligand 1 with other Lewis acids was also explored. Higher yields (50-85%) with moderate to good enantioselectivities (30-80%) were achieved for a variety of N-diphenylphosphinoyl ketimines.
- Chen, Yi-Jing,Chen, Chinpiao
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experimental part
p. 2201 - 2209
(2009/04/05)
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- Probing the importance of the hemilabile site of bis(phosphine) monoxide ligands in the copper-catalyzed addition of diethylzinc to N-phosphinoylimines: Discovery of new effective chiral ligands
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(Chemical Equation Presented) The hemilabile ligand Me-DuPHOS(O) 2 has proven to be a successful ligand for the copper-catalyzed addition of diethylzinc to N-phosphinoylimines. The corresponding α-chiral amines were obtained in high yields (80-98%) and enantiomeric ratios (19.0:1 to 99.0:1 er). Furthermore, this Cu?2 catalytic system has been shown to be effective in the addition of diethylzinc to nitroalkenes and in the reduction of β,β-disubstituted vinyl phenyl sulfones. This paper describes a general structure/selectivity study in which the three ligand subunits (chiral phospholane-linker-labile coordinating group (Z)) are systematically modified and tested in the copper-catalyzed addition of diethylzinc to the N-phosphinoylimine 1 derived from benzaldehyde. This study led to the discovery of a new class of effective chiral ligands that combine a chiral phospholane unit and an achiral phosphine oxide.
- Bonnaventure, Isabelle,Charette, Andre B.
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p. 6330 - 6340
(2008/12/22)
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- A convenient and practical method for the synthesis of N-thiophosphoryl aldimines and ketimines
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A convenient and practical method for the preparation of N-thiophosphoryl imines was developed through the thermal condensation of acetals with different thiophosphoramides at 120160°C.
- Xu, Xinyuan,Wang, Chungui,Zhou, Zhenghong,Zeng, Zebing,Xinpeng, Ma,Zhao, Guofeng,Tang, Chuchi
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p. 238 - 244
(2008/09/19)
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- Enantioselective aza-Henry reactions assisted by ZnII and N-methylephedrine
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(Chemical Equation Presented) Hooray aza-Henry! A combination of zinc triflate, an amine base, and (-)-N-methylephedrine (NME), which can be easily recovered and reused, leads to high enantioselectivities in the aza-Henry reaction of N-Boc-protected aldimines and nitromethane (see scheme; Boc = tert-butyloxycarbonyl).
- Palomo, Claudio,Oiarbide, Mikel,Halder, Rajkumar,Laso, Antonio,Lopez, Rosa
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p. 117 - 120
(2007/10/03)
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- Diastereoselective addition of enantiopure lithium tert- butylsulfinylferrocene to imines
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(S)-terf-Butylsulfinylferrocene was submitted to ortho-metalation, and the corresponding lithium derivative was trapped by alkyl or aryl imines bearing various electron-withdrawing groups on the nitrogen atom (Ts, Dpp, Boc). New aminosulfoxides were obtai
- Grach, Guillaume,Santos, Jana Sopkova-De Oliveira,Lohier, Jean-Francois,Mojovic, Ljubica,Ple, Nelly,Turck, Alain,Reboul, Vincent,Metzner, Patrick
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p. 9572 - 9579
(2007/10/03)
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- Stereoselective synthesis of α-silylamines by the direct addition of silyl anions to activated imines
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(Chemical Equation Presented) A highly efficient stereoselective synthesis of unusual α-silylamines via a direct silyl anion addition reaction is reported. This approach is convergent and avoids any problematic aza-Brook shifts of the anionic intermediate
- Ballweg, David M.,Miller, Rebecca C.,Gray, Danielle L.,Scheidt, Karl A.
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p. 1403 - 1406
(2007/10/03)
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- Synthesis of N-diphenylphosphinoylimines using the Kresze reaction
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The synthesis of N-diphenylphosphinoylimines involving the treatment of aldehydes with P,P-diphenyl N-sulfmylphosphoramidate (Ph2P(O)NSO) is described. The reagent is prepared from P,P-diphenylphosphinic amide, thionyl chloride, and imidazole.
- Lauzon, Caroline,Desrosiers, Jean-Nicolas,Charette, Andre B.
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p. 10579 - 10580
(2007/10/03)
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- The first catalytic asymmetric nitro-Mannich-type reaction promoted by a new heterobimetallic complex
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The best ratio is 1:1:3 for the components Yb, K, and binaphthol in the new heterobimetallic complex, which efficiently catalyzes an asymmetric nitro-Mannich-type reaction. The desired nitro-Mannich products 2 are obtained with up to 91% ee starting from
- Yamada, Ken-Ichi,Harwood, Simon J.,Groeger, Harald,Shibasaki, Masakatsu
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p. 3504 - 3506
(2007/10/03)
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- The titanium tetrachloride induced synthesis of N-phosphinoylimines and N-sulphonylimines directly from aromatic aldehydes
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The reaction of phosphinic amides or sulphonamides with an aromatic aldehyde in the presence of titanium tetrachloride and triethylamine provides a simple, one-step preparation of N-phosphinoylimines (5a-e) and N-sulphonylimines (7a-g). The extension of this reaction to ketones failed to give the desired imines, the aldol condensation products were obtained instead. The reaction of (+)-camphor with phosphinic amides or sulphonamides in refluxing toluene in the presence of titanium tetrachloride and triethylamine affords the (-)-camphorphosphinoyl- and (-)-camphorsulphonylimines in moderate yield.
- Jennings, W. Brian,Lovely, Carl J.
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p. 5561 - 5568
(2007/10/02)
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- Imines and Derivatives. Part 20. N-Phosphinoyloxaziridines: Synthesis and Structural Characterisation by Nuclear Magnetic Resonance Spectroscopy and a Crystal Structure of 3-(4-Chlorophenyl)-2-(diphenylphosphinoyl)oxaziridine
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The preparation of a new class of oxaziridines containing an N-phosphinoyl group is described.The compounds were obtained by peroxyacid oxidation of N-phosphinoyl imines under basic or neutral conditions, and characterised by n.m.r. spectroscopy.Revelant 2JPC, 3JPH, and 1JCH coupling constants are reported.An X-ray structure analysis of the title compound establishes that the 2-diphenylphosphinoyl group is trans to the 3-aryl ring.The P-N bond length (1.76 Angstroem) is abnormally high for an aminophosphorus(v) compound and the nitrogen atom is pyramidal (ΣN=280 deg).This geometry is interpreted in terms of an unusually low degree of ?-bonding between nitrogen and phosphorus due to the high s-character of the nitrogen lone pair.
- Boyd, Derek R.,Malone, John F.,McGuckin, M. Rosaleen,Jennings, W. Brian,Rutherford, Mark,Saket, Barahman M.
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p. 1145 - 1150
(2007/10/02)
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- AN EFFICIENT METHOD FOR THE PREPARATION OF N-PHOSPHINOYL AND N-SULPHONYL IMINES DIRECTLY FROM AROMATIC ALDEHYDES
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Reaction of phosphinamides and sulphonamides with aromatic aldehydes at 0 deg C in the presence of titanium tetrachloride and triethylamine provides a simple one-step preparation of N-phosphinoyl and N-sulphonyl imines.
- Jennings, W. Brian,Lovely, Carl J.
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p. 3725 - 3728
(2007/10/02)
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- N-Phosphinoyl Oxaziridines; A New Class of Oxaziridines
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Novel stable N-phosphionoyl oxaziridines have been prepared and characterised by n.m.r. and mass spectrometry; they function as oxidants towards phospines, sulphides, and alkenes
- Boyd, Derek R.,Jennings, W. Brian,McGuckin, Rosaleen M.,Rutherford, Mark,Saket, Barahman M.
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p. 582 - 583
(2007/10/02)
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