- Ni(0)-Catalyzed Synthesis of Polycyclic α,β-Unsaturated γ-Lactams via Intramolecular Carbonylative Cycloaddition of Yne-imines with CO
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A Ni(0)-catalyzed intramolecular carbonylative cycloaddition between 1,5-yne-imines and carbon monoxide (CO) is disclosed. When Ni(CO) 3 PCy 3 was employed as a pre-catalyst, a variety of polycyclic α,β-unsaturated γ-lactams were prepared in up to 78% yield with 100% atom efficiency. Aza-nickelacycles, generated by the oxidative cyclization of yne-imines on the Ni(0) center, were experimentally confirmed as key intermediates. Moreover, diastereoselective transformations of the obtained products to afford highly substituted polycyclic γ-lactams with three contiguous carbon stereocenters are reported.
- Ashida, Keita,Hoshimoto, Yoichi,Ogoshi, Sensuke
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- Efficient Synthesis of Polycyclic γ-Lactams by Catalytic Carbonylation of Ene-Imines via Nickelacycle Intermediates
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The nickel(0)-catalyzed carbonylative cycloaddition of 1,5- and 1,6-ene-imines with carbon monoxide (CO) is reported. Key to this reaction is the efficient regeneration of the catalytically active nickel(0) species from nickel carbonyl complexes such as [Ni(CO)3L]. A variety of tri- and tetracyclic γ-lactams were thus prepared in excellent yields with 100 % atom efficiency. Preliminary results on asymmetric derivatives promise potential in the synthesis of enantioenriched polycyclic γ-lactams.
- Hoshimoto, Yoichi,Ashida, Keita,Sasaoka, Yukari,Kumar, Ravindra,Kamikawa, Ken,Verdaguer, Xavier,Riera, Antoni,Ohashi, Masato,Ogoshi, Sensuke
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supporting information
p. 8206 - 8210
(2017/06/30)
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- [3+3] cyclodimerization of methylenecyclopropanes: Stoichiometric and catalytic reactions of Nickel(0) with electron-deficient alkylidenecyclopropanes
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Stoichiometric treatment of Ni(cod)2 with ethyl cyclopropylideneacetate (ECPA) in the presence of PCy3 resulted in an unpredicted formation of a Ni(0) complex bearing an (E,E)-1,2-bis(exo- alkylidene)cyclohexane ligand, which stemmed from the [3 + 3] cyclodimerization of ECPA. The reaction could be expanded to a Ni(0)-catalyzed [3 + 3] cyclodimerization reaction of ester-substituted methylenecyclopropanes, giving the corresponding cyclohexane derivatives in excellent yields.
- Ohashi, Masato,Taniguchi, Tomoaki,Ogoshi, Sensuke
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p. 2386 - 2389
(2010/08/05)
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- Nickeladihydrofuran. Key intermediate for nickel-catalyzed reaction of alkyne and aldehyde
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The formation of a nickeladihydrofuran by oxidative cyclization of an alkyne and an aldehyde with nickel(0) has been demonstrated; the transformation of the nickeladihydrofuran into an enone by decomposition, a lactone by carbonylation and an allylic alcohol by treatment with ZnMe2 suggests that nickeladihydrofuran is an important key intermediate in a variety of catalytic reactions. The Royal Society of Chemistry.
- Ogoshi, Sensuke,Arai, Tomoya,Ohashi, Masato,Kurosawa, Hideo
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p. 1347 - 1349
(2008/12/21)
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- Formation of an aza-nickelacycle by reaction of an imine and an alkyne with nickel(0): Oxidative cyclization, insertion, and reductive elimination
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(Chemical Equation Presented) Cyclize, add, reduce: The oxidative cyclization of an imine and an alkyne with nickel(0) followed by the insertion of a second alkyne gives a seven-membered aza-nickelacycle (see scheme). Subsequent reductive elimination yiel
- Ogoshi, Sensuke,Ikeda, Haruo,Kurosawa, Hideo
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p. 4930 - 4932
(2008/02/08)
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- Formation of nickeladihydropyran by oxidative addition of cyclopropyl ketone. Key intermediate in nickel-catalyzed cycloaddition
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Cyclopropyl phenyl ketone underwent oxidative addition to Ni(PCy3) generated from Ni(cod)2 and PCy3 to give a nickeladihydropyran, which is a key intermediate for the Ni(0)-catalyzed homo- or heterocycloaddition to give cyclopentane compounds having two carbonyl substituents at the 1,3-position. Copyright
- Ogoshi, Sensuke,Nagata, Midue,Kurosawa, Hideo
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p. 5350 - 5351
(2007/10/03)
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- Reversible carbon-carbon bond formation between 1,3-dienes and aldehyde or ketone on nickel(0)
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The reversible oxidative cyclization of dienes and aldehydes with nickel(0) proceeded to give η3:η1-allylalkoxynickel complexes. The treatment of these complexes with carbon monoxide led to the formation of the corresponding lactone and/or the regeneration of a butadiene and an aldehyde concomitant with the formation of Ni(CO)3(PCy 3). The scission of the nickel-oxygen bond of the allylalkoxy complexes with ZnMe2 leading to η3-allyl(methyl)nickel was very efficient to suppress the reverse reaction of the oxidative cyclization. The methylated η3-allylnickel compound underwent the reductive elimination. The carbonylative coupling reaction of the η3-allyl(methyl)nickel proceeded as well under a carbon monoxide atmosphere. Similarly, the addition of Me3SiCl to η3:η1-allylalkoxynickel complexes was also efficient for the inhibition of the reverse reaction. The resulting η3-1-siloxyethylallylnickel complex was treated with carbon monoxides followed by the addition of MeOH to give the expected hydroxyester. This method is efficient as well even for the η3: η1-allyl(alkoxy)nickel complex containing acetone as a component, which was so prone to undergo the reverse reaction hampering its isolation. The isolation of the η3:η1-allylalkoxynickel complex containing ketone as a component was made easier by the use of heavier butadiene and ketone, such as 2,3-dibenzyl-1,3-butadiene and benzophenone or by the use of cyclobutanone. The reaction with styrene oxide gave the η3: η1-allylalkoxynickel containing phenylacetoaldehyde, an isomer of styrene oxide.
- Ogoshi, Sensuke,Tonomori, Kei-Ichi,Oka, Masa-Aki,Kurosawa, Hideo
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p. 7077 - 7086
(2007/10/03)
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- Direct observation of oxidative cyclization of η2-alkene and η2-aldehyde on Ni(0) center. Significant acceleration by addition of Me3SiOTf
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Direct oxidative cyclization of (η2:η2-CH2CHCH2C6H4CHO)Ni(PR3) to form the nickelacycle and drastic acceleration of the cyclization by the addition of Me3SiOTf were ob
- Ogoshi, Sensuke,Oka, Masa-Aki,Kurosawa, Hideo
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p. 11802 - 11803
(2007/10/03)
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- Bioinorganic chemistry of nickel and carbon dioxide: An Ni complex behaving as a model system for carbon monoxide dehydrogenase enzyme
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In this paper we report the results of our studies on Ni complexes, the chemistry of which is relevant to the carbon monoxide dehydrogenase (CODH) enzyme of acetogenic bacteria. A single Ni system is able to promote both the reduction of carbon dioxide to carbon monoxide and the subsequent coupling of bound CO with an olefin and a thio group to afford an organic thioester, mimicking the enzyme activity.
- Tommasi, Immacolata,Aresta, Michele,Giannoccaro, Potenzo,Quaranta, Eugenio,Fragale, Carlo
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- Comparative studies on reactions of α,β- and β,γ-unsaturated amides and acids with nickel(0), palladium(0), and platinum(0) complexes. Preparation of new five- and six-membered nickel- and palladium-containing cyclic amide and ester complexes
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Reactivities of α,β- and β,γ-unsaturated amides as well as acids with zerovalent nickel, palladium, and platinum complexes have been compared. α,β-Unsaturated amides and acids form nickel-containing five-membered cyclic amide and ester complexes, (PR3)NiCH2CH(CH3)CONH (PR3 = PCy3, PEt3, P(t-Bu)2Et, dppe, dppp, dppb) and (PCy3)NiCH2CH(CH3)COO. β,γ-Unsaturated amides and acids afford nickel-containing six-membered cyclic amide and ester complexes, (PCy3)NiCH2CH2CH2CONH and (PCy3)NiCH2CH2CH2COO, whereas the palladium-containing six-membered cyclic ester complex (PCy3)PdCH2CH2CH2COO has been obtained from Pd(PCy3)2 and 3-butenoic acid. Pt(cod)2 in the presence of PCy3 reacted with methacrylamides to give olefin-coordinated Pt(0) complexes, Pt(PCy3)(CH2=C(CH3)CONHR)2 (R = H, Ph), whereas the reaction with α,β- and β,γ-unsaturated acids gave oxidative-addition products of the acids, trans-PtH(O2CR)(PCy3)2 (R = -C(CH3)=CH2, -CH2CH=CH2). An X-ray crystallographic analysis of one of the five-membered nickel-containing cyclic amides [(PEt3)NiCH2CH(CH3)CONH]4, was carried out. A novel tetrameric cyclic structure containing a nickelacyclic amide framework linked through Ni-O bonds with adjacent amide carbonyl groups has been established. Treatment of the nickel- and palladium-containing five- and six-membered cyclic amide and ester complexes with CO liberated cyclic imides and anhydrides. Thermolysis and reactions of the nickelacyclic complexes with AlCl3 and maleic anhydride led to β-elimination reactions with release of unsaturated amides and acids.
- Yamamoto, Takakazu,Sano, Kenji,Osakada, Kohtaro,Komiya, Sanshiro,Yamamoto, Akio,Kushi, Yoshihiko,Tada, Toshiji
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p. 2396 - 2403
(2008/10/08)
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- Mono- and Bis(ethyne)nickel(0) Complexes
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Various (ligand)nickel(0)-ethene complexes react with ethyne in ether or pentane at low temperature to afford crystalline compounds of types (R3P)2Ni(C2H2), 2Ni(C2H2), (tBuNC)2Ni(C2H2), (R3P)Ni(C2H2)(C2H4), 2(μ-C2H2), (R
- Poerschke, Klaus-Richard
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p. 5691 - 5699
(2007/10/02)
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- TRANSITION METAL ALLYLS VI. THE STOICHIOMETRIC REACTION OF 1,3-DIENES WITH LIGAND MODIFIED ZEROVALENT-NICKEL SYSTEMS
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Butadiene and methylsubstituted 1,3-dienes react with zerovalent-nickel-ligand complexes in a stoichiometric manner to give octadiendylnickel-ligand complexes.The structure, rearrangement and reactions with CO and P-donor ligands of these species have been studied with the help of 1H and 13C NMR spectroscopy.The results provide an insight into the mechanism of the nickel-catalyesd cyclodimerization of 1,3-dienes.
- Benn, R.,Buessemeier, B.,Holle, S.,Jolly, P. W.,Mynott, R.,et all.
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- PREPARATION OF SEVERAL NEW Ni- OR Pd-CONTAINING CYCLIC AMIDE AND ESTERS, (PR3)nNi(CH2CH2CH2COZ) (Z=NH, O) AND PCy3Pd(CH2CH2CH2COO), AND RING CONTRACTION OF THE SIX-MEMBERED Ni-CONTAINING CYCLIC ESTER TO ITS FIVE-MEMBERED ISOMER
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New metallacyclic amide and esters (PCy3Ni(CH2CH2CH2CONH), (PR3)nNi(CH2CH2CH2COO), PCy3Pd(CH2CH2CH2COO) ) have been prepared by reactions of zero-valent nickel and palladium complexes with unsaturated amide and acid.The 6-membered Ni-containing cyclic ester undergoes a ring contraction reaction to a 5-membered isomer.
- Sano, Kenji,Yamamoto, Takakazu,Yamamoto, Akio
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p. 695 - 698
(2007/10/02)
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- CARBONYLATION OF CYANO(PHENYL)BISLIGAND-NICKEL(II) COMPLEXES AND RELATED REACTIONS OF BENZOYL CYANIDE WITH NICKEL(O) COMPLEXES
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Carbonylation of the complexes Ni(CN)(C6H5)(P)2 (P=P(C2H5)3; P(cyclo-C6H11)3; 0.5(C2H5)2P-(CH2)4-P(C2H5)2) affords the acyl-derivatives Ni(CN)-(COC6H5)(P)n (n=1,2) which, in the presence of excess CO, undergo reductive elimination of C6H5COCN.It has been
- Favero, G.
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p. 225 - 232
(2007/10/02)
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