Nobuaki Kambe

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Organization: Osaka University

Department: Department of Applied Chemistry, Graduate School of Engineering

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Organic Chemistry

allene

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References

Co-Catalyzed Cross-Coupling Reaction of Alkyl Fluorides with Alkyl Grignard Reagents

Co-reporter:Takanori Iwasaki, Koji Yamashita, Hitoshi Kuniyasu, and Nobuaki Kambe

Organic Letters July 21, 2017 Volume 19(Issue 14) pp:3691-3691

Publication Date(Web):July 7, 2017

DOI:10.1021/acs.orglett.7b01370

The cross-coupling reaction of unactivated alkyl fluorides with alkyl Grignard reagents by a CoCl2/LiI/1,3-pentadiene catalytic system is described. The present reaction smoothly cleaved C–F bonds under mild conditions and achieved alkyl–alkyl cross-coupling even when sterically hindered tertiary alkyl Grignard reagents were employed. Since alkyl fluorides are inert toward many reagents and catalytic intermediates, the use of the present reaction enables a new multistep synthetic route to construct carbon frameworks by combining conventional transformations.

Multicomponent Coupling Reaction of Perfluoroarenes with 1,3-Butadiene and Aryl Grignard Reagents Promoted by an Anionic Ni(II) Complex

Co-reporter:Takanori Iwasaki, Asuka Fukuoka, Xin Min, Wataru Yokoyama, Hitoshi Kuniyasu, and Nobuaki Kambe

Organic Letters 2016 Volume 18(Issue 19) pp:4868-4871

Publication Date(Web):September 9, 2016

DOI:10.1021/acs.orglett.6b02343

An anionic Ni complex was isolated and its structure determined by X-ray crystallography. With such an anionic complex as a key intermediate, a regio- and stereoselective multicomponent coupling reaction of perfluoroarenes, aryl Grignard reagents, and 1,3-butadiene in a 1:1:2 ratio was achieved, resulting in the formation of 1,6-octadiene derivatives containing two aryl groups, one from the perfluoroarene and the other from the aryl Grignard reagent, at the 3- and 8-positions, respectively.

Nickel-catalyzed synthesis of diarylsulfides and sulfones via C–H bond functionalization of arylamides

Co-reporter:Vutukuri Prakash Reddy, Renhua Qiu, Takanori Iwasaki and Nobuaki Kambe

Organic & Biomolecular Chemistry 2015 vol. 13(Issue 24) pp:6803-6813

Publication Date(Web):13 May 2015

DOI:10.1039/C5OB00149H

The direct sulfenylation and sulfonylation of (sp2)C–H bonds of benzamide derivatives were achieved using a Ni catalyst with the aid of an 8-aminoquinoline moiety as a bidentate directing group. These protocols represent a convenient route for the formation of valuable diaryl sulfides and sulfones in moderate to excellent yields.

Copper-mediated thiolation of carbazole derivatives and related N-heterocycle compounds

Co-reporter:Longzhi Zhu, Xin Cao, Renhua Qiu, Takanori Iwasaki, Vutukuri Prakash Reddy, Xinhua Xu, Shuang-Feng Yin and Nobuaki Kambe

RSC Advances 2015 vol. 5(Issue 49) pp:39358-39365

Publication Date(Web):20 Apr 2015

DOI:10.1039/C5RA04965B

The copper-mediated direct thiolation of carbazole derivatives with disulfides via C(sp2)–H bond cleavage was developed for synthesizing diaryl and alkyl aryl sulfides. This reaction exhibits wide tolerance toward various functional groups giving the products in good yields without any additives or ligands, and can be easily extended to the synthesis of thioethers carrying a benzo[h]quinolone, 2-phenylquinoline, or indole moiety in satisfactory yields.

AlCl3-catalyzed insertion of isocyanides into nitrogen–sulfur bonds of sulfenamides

Co-reporter:Daisuke Shiro, Shin-ichi Fujiwara, Susumu Tsuda, Takanori Iwasaki, Hitoshi Kuniyasu, Nobuaki Kambe

Tetrahedron Letters 2015 Volume 56(Issue 12) pp:1531-1534

Publication Date(Web):18 March 2015

DOI:10.1016/j.tetlet.2015.01.096

Lewis acid-catalyzed insertion of isocyanides 2 into nitrogen–sulfur bonds of sulfenamides 1 was developed. This method provided a convenient method for the synthesis of isothioureas 3. Among Lewis acids examined, AlCl3 brought about the best result. Acetic acid assisted one-pot preparation of unsymmetrical ureas was also described.

Regioselective Cis Insertion of DMAD into Au–P Bonds: Effect of Auxiliary Ligands on the Reaction Mechanism

Co-reporter:Hitoshi Kuniyasu, Takuya Nakajima, Takashi Tamaki, Takanori Iwasaki, and Nobuaki Kambe

Organometallics 2015 Volume 34(Issue 7) pp:1373-1376

Publication Date(Web):April 1, 2015

DOI:10.1021/acs.organomet.5b00078

The cis insertion of dimethyl acetylenedicarboxylate (DMAD, 2) into the Au–P bond of Au(SAr)(PAr′3) (1) occurs selectively at room temperature to give adduct 3, whose X-ray crystallographic analysis exhibits the predominant character of an alkenylphosphorus zwitterion complex. The first-order kinetics with respect to 1 and 2 and the large negative value of ΔS⧧ indicate that the reaction proceeds through the coordination of 2 to 1 followed by a concerted inner-sphere nucleophilic attack of PPh3 on the coordinated triple bond. In contrast, Au(Cl)(PPh3) (4) does not react with 2 even at 60 °C. However, the tricoordinated 16-electron complex Au(Cl)(PPh3)2 (5) quite successfully reacts with 2 to produce insertion product 6, demonstrating that two PPh3 ligands are required for the reaction.

The Palladium-Catalyzed Intermolecular C–H Chalcogenation of Arenes

Co-reporter:Renhua Qiu, Vutukuri Prakash Reddy, Takanori Iwasaki, and Nobuaki Kambe

The Journal of Organic Chemistry 2015 Volume 80(Issue 1) pp:367-374

Publication Date(Web):December 1, 2014

DOI:10.1021/jo502402d

Palladium catalyzes the intermolecular chalcogenation of carbazole, 2-phenylpyridine, benzo[h]quinolone, and indole derivatives with disulfides and diselenides via selective C–H bond cleavage, providing a convenient route to thio and selenoethers.

Diarylrhodates as Promising Active Catalysts for the Arylation of Vinyl Ethers with Grignard Reagents

Co-reporter:Takanori Iwasaki ; Yoshinori Miyata ; Ryo Akimoto ; Yuuki Fujii ; Hitoshi Kuniyasu

Journal of the American Chemical Society 2014 Volume 136(Issue 26) pp:9260-9263

Publication Date(Web):June 17, 2014

DOI:10.1021/ja5043534

Anionic diarylrhodium complexes, generated by reacting [RhCl(cod)]2 with 2 equiv of aryl Grignard reagents, were found to be effective active catalysts in cross-coupling reactions of vinyl ethers with aryl Grignard reagents, giving rise to the production of vinyl arenes. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar–O or Ar–Br bonds. A lithium rhodate complex was isolated, and its crystal structure was determined by X-ray crystallography.

Halogen exchange by reaction of CpRu(Cl)(PPh3)2 with MeC(O)X (X = Br, I) and its mechanistic study

Co-reporter:Hitoshi Kuniyasu, Atsushi Sanagawa, Takuya Nakajima, Takanori Iwasaki, Nobuaki Kambe, Karan Bobuatong, Masahiro Ehara

Journal of Organometallic Chemistry 2014 Volume 769() pp:34-37

Publication Date(Web):15 October 2014

DOI:10.1016/j.jorganchem.2014.06.018

•The ligand exchange between CpRu(Cl)(PPh3)2 and MeC(O)X successfully takes place.•The reaction mechanism is investigated by DFT calculation and experiments.•A radical species is proposed to participate in the reaction.The treatment of CpRu(Cl)(PPh3)2 with MeC(O)X offers a very convenient procedure for the synthesis of CpRu(X)(PPh3)2. The proposed mechanism involves an intermediate produced by the concerted liberation of PPh3 by the incoming MeC(O)X and the subsequent subtraction of the X atom by the Ru atom to form a radical pair.The treatment of CpRu(Cl)(PPh3)2 with MeC(O)X offers a very convenient procedure for the synthesis of CpRu(X)(PPh3)2. The proposed mechanism involves an intermediate produced by the concerted liberation of PPh3 by the incoming MeC(O)X and the subsequent subtraction of the X atom by the Ru atom to form a radical pair.

Palladium-Catalyzed Decarbonylative Rearrangement of N-Allenyl Seleno- and Tellurocarbamates

Co-reporter:Daisuke Shiro;Hiroyuki Nagai;Shin-ichi Fujiwara;Susumu Tsuda;Takanori Iwasaki;Hitoshi Kuniyasu

Heteroatom Chemistry 2014 Volume 25( Issue 6) pp:518-524

Publication Date(Web):

DOI:10.1002/hc.21217

ABSTRACT

Decarbonylative rearrangement of seleno- and tellurocarbamates carrying an allenyl group on the nitrogen was found to proceed in the presence of a palladium catalyst to afford 3-chalcogeno-1-azadienes. This transformation may involve oxidative addition of Pd to a carbon–chalcogen bond, decarbonylation from a carbamoylpalladium unit (R₂N-C(O)-PdChPh: Ch = Se or Te), Pd shift, and reductive elimination.

Copper-Catalyzed Alkyl–Alkyl Cross-Coupling Reactions Using Hydrocarbon Additives: Efficiency of Catalyst and Roles of Additives

Co-reporter:Takanori Iwasaki, Reiko Imanishi, Ryohei Shimizu, Hitoshi Kuniyasu, Jun Terao, and Nobuaki Kambe

The Journal of Organic Chemistry 2014 Volume 79(Issue 18) pp:8522-8532

Publication Date(Web):July 3, 2014

DOI:10.1021/jo501006u

Cross-coupling of alkyl halides with alkyl Grignard reagents proceeds with extremely high TONs of up to 1230000 using a Cu/unsaturated hydrocarbon catalytic system. Alkyl fluorides, chlorides, bromides, and tosylates are all suitable electrophiles, and a TOF as high as 31200 h–1 was attained using an alkyl iodide. Side reactions of this catalytic system, i.e., reduction, dehydrohalogenation (elimination), and the homocoupling of alkyl halides, occur in the absence of additives. It appears that the reaction involves the β-hydrogen elimination of alkylcopper intermediates, giving rise to olefins and Cu–H species, and that this process triggers both side reactions and the degradation of the Cu catalyst. The formed Cu–H promotes the reduction of alkyl halides to give alkanes and Cu–X or the generation of Cu(0), probably by disproportionation, which can oxidatively add to alkyl halides to yield olefins and, in some cases, homocoupling products. Unsaturated hydrocarbon additives such as 1,3-butadiene and phenylpropyne play important roles in achieving highly efficient cross-coupling by suppressing β-hydrogen elimination, which inhibits both the degradation of the Cu catalyst and undesirable side reactions.

Co-Catalyzed Cross-Coupling of Alkyl Halides with Tertiary Alkyl Grignard Reagents Using a 1,3-Butadiene Additive

Co-reporter:Takanori Iwasaki ; Hiroaki Takagawa ; Surya P. Singh ; Hitoshi Kuniyasu

Journal of the American Chemical Society 2013 Volume 135(Issue 26) pp:9604-9607

Publication Date(Web):June 19, 2013

DOI:10.1021/ja404285b

The cobalt-catalyzed cross-coupling of alkyl (pseudo)halides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor and LiI is described. Sterically congested quaternary carbon centers could be constructed by using tertiary alkyl Grignard reagents. This reaction proceeds via an ionic mechanism with inversion of stereochemistry at the reacting site of the alkyl halide and is compatible with various functional groups. The use of both 1,3-butadiene and LiI was essential for achieving high yields and high selectivities.

Rhodium-Catalyzed Intermolecular Oxidative Cross-Coupling of (Hetero)Arenes with Chalcogenophenes

Co-reporter:Vutukuri Prakash Reddy, Renhua Qiu, Takanori Iwasaki, and Nobuaki Kambe

Organic Letters 2013 Volume 15(Issue 6) pp:1290-1293

Publication Date(Web):February 26, 2013

DOI:10.1021/ol400230y

A straightforward and efficient method for the rhodium-catalyzed intermolecular oxidative cross-coupling of arenes and heteroarenes with thio- and selenophene derivatives (chalcogenophenes) via double C–H bond cleavage has been developed by using Cu(OAc)2/AgSbF6 as an oxidant. The reaction is applicable to a wide range of (hetero)arenes carrying a directing group and chalcogenophenes to yield substituted biaryl heterocyclic derivatives and oligothiophene derivatives in moderate to high yields.

Synthesis of imidazo and benzimidazo[2,1-a]isoquinolines by rhodium-catalyzed intramolecular double C–H bond activation

Co-reporter:Vutukuri Prakash Reddy, Takanori Iwasaki and Nobuaki Kambe

Organic & Biomolecular Chemistry 2013 vol. 11(Issue 14) pp:2249-2253

Publication Date(Web):28 Feb 2013

DOI:10.1039/C3OB27396B

The rhodium-catalyzed intramolecular direct arylation of imidazole and benzimidazole derivatives via double C–H bond activation is described. This approach provides new access to a wide range of imidazo and benzimidazo[2,1-a]isoquinoline derivatives in moderate to high yields. This reaction provides an alternative method to the known Pd-catalyzed intramolecular oxidative cross-coupling reactions.

σ-Bond Metathesis between M–X and RC(O)X′ (M = Pt, Pd; X, X′ = Cl, Br, I): Facile Determination of the Relative ΔG Values of the Oxidative Additions of RC(O)X to an M(0) Complex, Evidence by Density Functional Theory Calculations, and Synthetic Applications

Co-reporter:Hitoshi Kuniyasu, Atsushi Sanagawa, Daisuke Nakane, Takanori Iwasaki, Nobuaki Kambe, Karan Bobuatong, Yunpeng Lu, and Masahiro Ehara

Organometallics 2013 Volume 32(Issue 6) pp:2026-2032

Publication Date(Web):March 13, 2013

DOI:10.1021/om400157a

The novel utility of the ligand exchange reaction between M–X and RC(O)X′ (X, X′ = halogen; R = aryl, alkyl) is described. The relative ΔGs (ΔΔGs) of the oxidative additions of acid halides RC(O)X to M(PPh3)2Ln (M = Pt, Pd) were determined using the halogen-exchange reactions between X of trans-M(X)[C(O)R](PPh3)2 and X′ of RC(O)X′. Experimental thermodynamics data are reasonably consistent with those obtained by density functional theory (DFT) calculations. Activation parameters obtained by experiments as well as a systematic DFT study supported the fact that reactions occurred through slightly distorted quadrangular pentacoordinated σ-bond metatheses, in which the Cl atom underwent a more indirect course than the Br atom. Moreover, exchange reactions were employed as the accessible prototype for the conversion of halogen ligands of nickel triad complexes into heavier halogen ligands.

NickelButadiene Catalytic System for the Cross-Coupling of Bromoalkanoic Acids with Alkyl Grignard Reagents: A Practical and Versatile Method for Preparing Fatty Acids

Co-reporter:Dr. Takanori Iwasaki;Kiyokazu Higashikawa;Dr. Vutukuri P. Reddy;Willbe W. S. Ho;Dr. Yukari Fujimoto;Dr. Koichi Fukase;Dr. Jun Terao;Dr. Hitoshi Kuniyasu;Dr. Nobuaki Kambe

Chemistry - A European Journal 2013 Volume 19( Issue 9) pp:2956-2960

Publication Date(Web):

DOI:10.1002/chem.201204222

Nickel-Catalyzed Coupling of Thiomethyl-Substituted 1,3-Benzothiazoles with Secondary Alkyl Grignard Reagents

Co-reporter:Dr. Arash Ghaderi;Dr. Takanori Iwasaki;Asuka Fukuoka;Dr. Jun Terao;Dr. Nobuaki Kambe

Chemistry - A European Journal 2013 Volume 19( Issue 9) pp:2951-2955

Publication Date(Web):

DOI:10.1002/chem.201203413

Copper-catalyzed coupling reaction of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as an effective additive

Co-reporter:Ruwei Shen, Takanori Iwasaki, Jun Terao and Nobuaki Kambe

Chemical Communications 2012 vol. 48(Issue 74) pp:9313-9315

Publication Date(Web):13 Aug 2012

DOI:10.1039/C2CC34847K

Cu-catalyzed cross-coupling of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as a ligand precursor was developed. The use of 1,3-butadiene resulted in improved yields of alkyl–alkyl products with improved selectivities.

Palladium-catalyzed vinylselenation of allenes

Co-reporter:Shin-ichi Fujiwara, Maiko Okuyama, Susumu Tsuda, Takanori Iwasaki, Hitoshi Kuniyasu, Nobuaki Kambe

Tetrahedron 2012 68(51) pp: 10523-10529

Publication Date(Web):

DOI:10.1016/j.tet.2012.10.003

A Computational Study of Lithium Cuprate Mixed Aggregates

Co-reporter:Chau Nguyen Duy Khiem and Le Ngoc Thach, Takanori Iwasaki and Nobuaki Kambe , Andrey A. Boguslavskiy and Lawrence M. Pratt

The Journal of Physical Chemistry A 2012 Volume 116(Issue 36) pp:9027-9032

Publication Date(Web):August 24, 2012

DOI:10.1021/jp3034424

Lithium dialkylcuprates may potentially form mixed aggregates with many species in solution. Those include excess alkyllithium used to prepare the cuprate, lithium halide, and lithium cyanide from cuprate preparation and from coupling reactions with alkyl halides, higher order cuprates, and species resulting from incomplete cuprate reactions. The M06 DFT method was used to elucidate the structures and energies of formation of potential mixed aggregates. A comparison was made to available experimental data.

Pd-catalyzed cross-coupling reactions of alkyl halides

Co-reporter:Nobuaki Kambe, Takanori Iwasaki and Jun Terao

Chemical Society Reviews 2011 vol. 40(Issue 10) pp:4937-4947

Publication Date(Web):25 Jul 2011

DOI:10.1039/C1CS15129K

Cross-coupling reactions have become indispensable tools for creating carbon–carbon (or heteroatom) bonds in organic synthesis. Like in other important transition metal catalyzed reactions, such as metathesis, addition, and polymerization, unsaturated compounds are usually employed as substrates for cross-coupling reactions. However during the past decade, a great deal of effort has been devoted to the use of alkyl halides as saturated compounds in cross-coupling reactions, which has resulted in significant progress in this undeveloped area by introducing new effective ligands. Many useful catalytic systems are now available for synthetic transformations based on Csp3–Csp3, Csp3–Csp2 and Csp3–Csp bond formation as complementary methods to conventional Csp2–Csp2, Csp2–Csp and Csp–Csp coupling. This tutorial review summarizes recent advances in cross-coupling reactions of alkyl halides and pseudohalides catalyzed by a palladium complex.

Cross-coupling of Grignard reagents with alkyl halides or tosylates by the use of nickel or palladium containing perovskite

Co-reporter:Surya Prakash Singh, Takanori Iwasaki, Jun Terao, Nobuaki Kambe

Tetrahedron Letters 2011 Volume 52(Issue 7) pp:774-776

Publication Date(Web):16 February 2011

DOI:10.1016/j.tetlet.2010.12.011

Nickel and palladium-containing perovskites, LaFe0.8Ni0.2O3 (LFNO) and LaFe0.95Pd0.05O3 (LFPO), could be employed as effective catalyst sources for the cross-coupling of nonactivated alkyl halides and tosylates with Grignard reagents in the presence of conjugated dienes. The reaction proceeded efficiently at room temperature or below using only ca. 1 mol % of catalysts with respect to Ni or Pd and the perovskites were reused without considerable loss of activity.

Nickel-Catalyzed Alkyl Coupling Reactions: Evaluation of Computational Methods

Co-reporter:Lawrence M. Pratt, Stewart Voit, and Fabian N. Okeke and Nobuaki Kambe

The Journal of Physical Chemistry A 2011 Volume 115(Issue 11) pp:2281-2290

Publication Date(Web):February 25, 2011

DOI:10.1021/jp1077196

The B3LYP, M06, M06L, M062X, MPW1K, and PBE1PBE DFT methods were evaluated for modeling nickel-catalyzed coupling reactions. The reaction consists of a nucleophilic attack by a carbanion equivalent on the nickel complex, SN2 attack by the anionic nickel complex on an alkyl halide, and reductive elimination of the coupled alkane product, regenerating the nickel catalyst. On the basis of CCSD(T)//DFT single-point energies, the B3LYP, M06, and PBE1PBE functionals were judged to generate the best ground state geometries. M06 energies are generally comparable or superior to B3LYP and PBE1PBE energies for transition state calculations. The MP2 and CCSD methods were also evaluated for single-point energies at the M06 geometries. The rate-determining step of this reaction was found to be nucleophilic attack of a L2NiR anion on the alkyl halide.

Pd-Catalyzed Regioselective Iminothiolation of Alkynes: A Remarkable Effect of the CF3 Group of Iminosulfides

Co-reporter:Yasunori Minami, Hitoshi Kuniyasu, Atsushi Sanagawa and Nobuaki Kambe

Organic Letters 2010 Volume 12(Issue 17) pp:3744-3747

Publication Date(Web):August 10, 2010

DOI:10.1021/ol101289k

Pd-catalyzed iminothiolation of alkynes took place to afford 4-SR substituted 1-azadienes regioselectively.

Nickel-Catalyzed Regioselective Carbomagnesation of Methylenecyclopropanes through a Site-Selective CarbonCarbon Bond Cleavage

Co-reporter:Jun Terao Dr.;Masahiro Tomita;SuryaPrakash Singh Dr. Dr.

Angewandte Chemie International Edition 2010 Volume 49( Issue 1) pp:144-147

Publication Date(Web):

DOI:10.1002/anie.200904721

Synthesis of Organic-Soluble Conjugated Polyrotaxanes by Polymerization of Linked Rotaxanes

Co-reporter:Jun Terao ; Susumu Tsuda ; Yuji Tanaka ; Kento Okoshi ; Tetsuaki Fujihara ; Yasushi Tsuji

Journal of the American Chemical Society 2009 Volume 131(Issue 44) pp:16004-16005

Publication Date(Web):October 15, 2009

DOI:10.1021/ja9074437

Extensive research on the use of cyclodextrin for insulating π-conjugated polymer chains has been carried out. However, the resulting polyrotaxanes do not exhibit high and constant covering ratios and are generally insoluble in organic solvents. Here we demonstrate a new method of synthesizing permethylated cyclodextrin-based polyrotaxanes involving the polymerization of linked rotaxane monomers. The insulated molecular wires obtained by this method are highly soluble in organic solvents and have a high covering ratio, rigidity, and photoluminescence efficiency. A cholesteric liquid-crystal phase was observed for these highly rigid polyrotaxanes, in which threading of a π-conjugated polymer chain through chiral macrocycles occurs.

Ni-catalyzed regioselective three-component coupling of alkyl halides, arylalkynes, or enynes with R–M (M = MgX′, ZnX′)

Co-reporter:Jun Terao, Fumiaki Bando and Nobuaki Kambe

Chemical Communications 2009 (Issue 47) pp:7336-7338

Publication Date(Web):13 Oct 2009

DOI:10.1039/B918548H

A new method for the regioselective three-component cross-coupling of alkyl halides, alkynes, or enynes with organomagnesium or organozinc reagents in the presence of a nickel catalyst and a dppb ligand has been developed.

Non-catalytic conversion of C–F bonds of benzotrifluorides to C–C bonds using organoaluminium reagents

Co-reporter:Jun Terao, Misaki Nakamura and Nobuaki Kambe

Chemical Communications 2009 (Issue 40) pp:6011-6013

Publication Date(Web):22 Sep 2009

DOI:10.1039/B915620H

A facile method for the conversion of C–F bonds of benzotrifluorides to C–C bonds has been developed using aluminium reagents in the absence of catalysts.

Silver-catalyzed carbomagnesiation of terminal aryl and silylalkynes and enynes in the presence of 1,2-dibromoethane

Co-reporter:Yuuki Fujii, Jun Terao and Nobuaki Kambe

Chemical Communications 2009 (Issue 9) pp:1115-1117

Publication Date(Web):07 Jan 2009

DOI:10.1039/B820521C

Regioselective carbomagnesiation of terminal alkynes and enynes with alkylGrignard reagents has been achieved by the combined use of a silver catalyst and 1,2-dibromoethane.

Palladium-Catalyzed Intramolecular Selenocarbamoylation of Allenes with Carbamoselenoates: A New Entry to ,-Unsaturated Lactams

Co-reporter:Masashi Toyofuku;Erika Murase;Hiroyuki Nagai;Shin-ichi Fujiwara;Tsutomu Shin-ike;Hitoshi Kuniyasu

European Journal of Organic Chemistry 2009 Volume 2009( Issue 19) pp:3141-3144

Publication Date(Web):

DOI:10.1002/ejoc.200900319

Abstract

Pd(PPh₃)₄-catalyzed intramolecular selenocarbamoylation of allenes led to the regioselective formation of α,β-unsaturated five- and six-membered lactams having an allyl selenide unit. This procedure could be applied to the synthesis of the corresponding sulfur analogue by thiocarbamoylation as well as a cyclopentenone. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

Nickel-catalyzed cross-coupling of unactivated alkyl halides and tosylate carrying a functional group with alkyl and phenyl Grignard reagents

Co-reporter:Surya Prakash Singh, Jun Terao, Nobuaki Kambe

Tetrahedron Letters 2009 50(40) pp: 5644-5646

Publication Date(Web):

DOI:10.1016/j.tetlet.2009.07.094

Cu-catalyzed regioselective carbomagnesiation of dienes and enynes with sec- and tert-alkyl Grignard reagents

Co-reporter:Hirohisa Todo, Jun Terao, Hideyuki Watanabe, Hitoshi Kuniyasu and Nobuaki Kambe

Chemical Communications 2008 (Issue 11) pp:1332-1334

Publication Date(Web):11 Jan 2008

DOI:10.1039/B716678H

The carbomagnesiation of dienes and enynes with sec- and tert-alkyl Grignard reagents has been achieved by using copper salts as catalysts.

Titanocene-catalyzed alkylative dimerization of vinyl Grignard reagent using alkyl halides

Co-reporter:Yuuki Fujii, Jun Terao, Yuichiro Kato and Nobuaki Kambe

Chemical Communications 2008 (Issue 44) pp:5836-5838

Publication Date(Web):06 Oct 2008

DOI:10.1039/B813596G

Dimerization of vinyl Grignard reagents and concomitant alkylation with alkyl halides have been achieved by using Cp2TiCl2 as a catalyst.

Conversion of a (sp3)C–F bond of alkyl fluorides to (sp3)C–X (X = Cl, C, H, O, S, Se, Te, N) bonds using organoaluminium reagents

Co-reporter:Jun Terao, Shameem Ara Begum, Yoshiaki Shinohara, Masahiro Tomita, Yoshitaka Naitoh and Nobuaki Kambe

Chemical Communications 2007 (Issue 8) pp:855-857

Publication Date(Web):23 Nov 2006

DOI:10.1039/B613641A

A simple method for the conversion of (sp3)C–F bonds of alkyl fluorides to (sp3)C–X (X = Cl, C, H, O, S, Se, Te, N) bonds has been achieved by the use of a hexane solution of organoaluminum reagents having Al–X bonds.

Cross-coupling of alkyl halides with Grignard reagents using nickel and palladium complexes bearing η3-allyl ligand as catalysts

Co-reporter:Jun Terao, Yoshitaka Naitoh, Hitoshi Kuniyasu and Nobuaki Kambe

Chemical Communications 2007 (Issue 8) pp:825-827

Publication Date(Web):21 Nov 2006

DOI:10.1039/B612586G

The cross-coupling of Grignard reagents with alkyl bromides and tosylates has been achieved by the use of η3-allylnickel and η3-allylpalladium complexes as catalysts.

Transition metal catalyzed carbon-silicon bond forming reactions using chlorosilanes promoted by Grignard reagents

Co-reporter:Jun Terao

The Chemical Record 2007 Volume 7(Issue 1) pp:

Publication Date(Web):22 FEB 2007

DOI:10.1002/tcr.20101

New catalytic CSi bond-forming reactions using chlorosilanes are described. These reactions proceed efficiently under mild conditions by the combined use of Grignard reagents and transition metal catalysts, such as Ti, Zr, Ni, and Pd. It is proposed that ate complex intermediates formed by the reaction of transition metals with Grignard reagents play important roles as the active catalytic species. The present study demonstrates the practical use of chlorosilanes in transition metal catalyzed silylation reactions providing convenient methods for allyl- or vinylsilane synthesis. The reaction pathways of these transformations as well as the scope and limitations are discussed. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 57–67; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20101

Definitive Evidence for the Insertion of Terminal Alkynes into ArylSPt Bonds: “o-Halogen Effect” in Stoichiometric and Catalytic Reactions

Co-reporter:Hitoshi Kuniyasu Dr.;Fumikazu Yamashita;Jun Terao Dr.

Angewandte Chemie 2007 Volume 119(Issue 31) pp:

Publication Date(Web):6 JUL 2007

DOI:10.1002/ange.200604986

Eine unerwartete Beschleunigung der Insertion terminaler Alkine in die S-Pt-Bindung der Komplexe 1 wurde beobachtet, wenn ein ortho-Halogensubstituent in der SAr-Einheit vorlag (siehe Schema). Die Reaktionsgeschwindigkeiten waren für G=o-Cl, o-Br oder o-I viel höher als für elektronenschiebende oder elektronenziehende Gruppen. Dieser „ortho-Halogen-Effekt“ trat auch in der palladiumkatalysierten Addition von (ArS)₂ an Alkine auf.

Copper-Catalyzed Cross-Coupling Reaction of Grignard Reagents with Primary-Alkyl Halides: Remarkable Effect of 1-Phenylpropyne

Co-reporter:Jun Terao Dr.;Hirohisa Todo;Shameem Ara Begum;Hitoshi Kuniyasu Dr. Dr.

Angewandte Chemie 2007 Volume 119(Issue 12) pp:

Publication Date(Web):5 FEB 2007

DOI:10.1002/ange.200603451

Gelungene Verbindung: Die Cu-katalysierte Kreuzkupplung zwischen primären Alkylhalogeniden und primären, sekundären und tertiären Alkyl- sowie Phenyl-Grignard-Reagentien verläuft in THF unter Rückfluss in Gegenwart von 1-Phenylpropin effizient (siehe Schema). Die Reaktion gelingt auch mit Alkylmesylaten (OMs) und -tosylaten (OTs). Die Alkyl-X-Reaktivitäten gegenüber dem Grignard-Reagens nehmen in der Reihenfolge X=Cl<F<OMs<OTs<Br zu.

Copper-Catalyzed Cross-Coupling Reaction of Grignard Reagents with Primary-Alkyl Halides: Remarkable Effect of 1-Phenylpropyne

Co-reporter:Jun Terao Dr.;Hirohisa Todo;Shameem Ara Begum;Hitoshi Kuniyasu Dr. Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 12) pp:

Publication Date(Web):5 FEB 2007

DOI:10.1002/anie.200603451

A general get-together: The Cu-catalyzed cross-coupling reaction of primary-alkyl halides with primary-, secondary-, and tertiary-alkyl and phenyl Grignard reagents proceeds efficiently in THF under reflux in the presence of 1-phenylpropyne (see scheme). The reaction is also applicable to alkyl mesylates (OMs) and tosylates (OTs). The reactivities of alkylX with a Grignard reagent increase in the order X=Cl<F<OMs<OTs<Br.

Definitive Evidence for the Insertion of Terminal Alkynes into ArylSPt Bonds: “o-Halogen Effect” in Stoichiometric and Catalytic Reactions

Co-reporter:Hitoshi Kuniyasu Dr.;Fumikazu Yamashita;Jun Terao Dr.

Angewandte Chemie International Edition 2007 Volume 46(Issue 31) pp:

Publication Date(Web):6 JUL 2007

DOI:10.1002/anie.200604986

An unexpected acceleration of the insertion of terminal alkynes into the SPt bond of complexes 1 was observed when an o-halogen substituent was present in the SAr moiety (see scheme). The reaction rates for G=o-Cl, o-Br, or o-I were much greater than for electron-donating or electron-withdrawing groups. This “o-halogen effect” was also found to be relevant to the Pd-catalyzed addition of (ArS)₂ to alkynes.

“β-cis-SAr effect” on decarbonylation from α,β-unsaturated acyl and aroyl complexes

Co-reporter:Tomohiro Kato, Hitoshi Kuniyasu, Takamichi Kajiura, Yasunori Minami, Atsushi Ohtaka, Masanori Kinomoto, Jun Terao, Hideo Kurosawa and Nobuaki Kambe

Chemical Communications 2006 (Issue 8) pp:868-870

Publication Date(Web):18 Jan 2006

DOI:10.1039/B515616E

Lone pair of heteroatom located at the β-cis position in α,β-unsaturated acyl and aroyl group 10 metal complexes dramatically facilitated the stoichiometric and catalytic decarbonylation reactions.

Novel Nickel-Catalyzed Coupling Reaction of Allyl Ethers with Chlorosilanes, Alkyl Tosylates, or Alkyl Halides Promoted by Vinyl-Grignard Reagent Leading to Allylsilanes or Alkenes

Co-reporter:Jun Terao;Hiroyasu Watabe;Hiroyuki Watanabe

Advanced Synthesis & Catalysis 2004 Volume 346(Issue 13-15) pp:

Publication Date(Web):16 DEC 2004

DOI:10.1002/adsc.200404192

A new method for a carbon-silicon or carbon-carbon bond forming reaction between allyl ethers and chlorosilanes, alkyl tosylates, or alkyl halides giving rise to allylsilanes or alkenes has been developed. This reaction proceeds efficiently at ambient temperature by the combined use of nickel catalysts and a vinyl-Grignard reagent. A possible reaction pathway involving the formation of allyl-Grignard reagents via transmetallation of π-allylnickel complexes with the vinyl-Grignard reagent and subsequent trapping of the thus formed allyl-Grignard reagents with electrophiles is proposed.

Nickel-Catalyzed Regioselective Three Component Coupling Reaction of Alkyl Halides, Butadienes, and Ar-M (M=MgX, ZnX)

Co-reporter:Jun Terao;Shinsuke Nii;Firoz A. Chowdhury;Akifumi Nakamura

Advanced Synthesis & Catalysis 2004 Volume 346(Issue 8) pp:

Publication Date(Web):5 AUG 2004

DOI:10.1002/adsc.200404041

A new method for the regioselective three component cross-coupling reaction of alkyl halides, 1,3-butadienes, and aryl-Grignard reagents has been developed by the use of a nickel catalyst. This reaction proceeds efficiently at 25 °C using (dppf)NiCl₂ as a catalyst. Alkyl chlorides, bromides, and iodides can be used as suitable alkylating reagents. The reaction also proceeds when arylzinc halides are used instead of Grignard reagents. Competitive reactions of a mixture of primary, secondary, and tertiary alkyl bromides showed that the reactivities of the halides increase in the order primary<secondary<tertiary. A possible reaction pathway involving single electron transfer from a nickelate complex to alkyl halides is proposed.

Nickel-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Organozinc and Grignard Reagents with 1,3,8,10-Tetraenes as Additives

Co-reporter:Jun Terao Dr.;Hirohisa Todo;Hideyuki Watanabe;Aki Ikumi Dr.

Angewandte Chemie 2004 Volume 116(Issue 45) pp:

Publication Date(Web):17 NOV 2004

DOI:10.1002/ange.200460246

Die Additive bringen's: Die Zugabe von Bis(1,3-butadienyl)verbindungen (Tetraenen) war für die effiziente Ni-katalysierte Kupplung von Organozinkreagentien mit Alkylbromiden und einem Tosylat essenziell (siehe Schema, X=C(CO₂Me)₂ oder NCH₂Ph). Auch die Effizienz der Ni-katalysierten Kupplung eines Alkylfluorids mit einem Grignard-Reagens wurde durch diese Tetraene verbessert.

Nickel-Catalyzed Cross-Coupling Reaction of Alkyl Halides with Organozinc and Grignard Reagents with 1,3,8,10-Tetraenes as Additives

Co-reporter:Jun Terao Dr.;Hirohisa Todo;Hideyuki Watanabe;Aki Ikumi Dr.

Angewandte Chemie International Edition 2004 Volume 43(Issue 45) pp:

Publication Date(Web):17 NOV 2004

DOI:10.1002/anie.200460246

Essential additives: The addition of bis(1,3-butadienyl) compounds (tetraenes) was essential in the efficient Ni-catalyzed cross-coupling of organozinc reagents with alkyl bromides and a tosylate (see scheme, X=C(CO₂Me)₂ or NCH₂Ph). The efficiency of the Ni-catalyzed cross-coupling of an alkyl fluoride with a Grignard reagent was also improved by using these tetraenes.

Nickel-Catalyzed Dimerization and Carbosilylation of 1,3-Butadienes with Chlorosilanes and Grignard Reagents

Co-reporter:Jun Terao Dr.;Akihiro Oda;Aki Ikumi;Akifumi Nakamura;Hitoshi Kuniyasu Dr. Dr.

Angewandte Chemie 2003 Volume 115(Issue 29) pp:

Publication Date(Web):24 JUL 2003

DOI:10.1002/ange.200351579

Eine Mehrkomponenten-Kupplungsreaktion von 1,3-Butadienderivaten verläuft über Ni-katalysierte Dimerisierung gefolgt von einer Carbosilylierung mit einem Chlorsilan und einem Grignard-Reagens (siehe Schema; R=H, Me oder C₉H₁₉; R′, R′′=Kohlenwasserstoffsubstituent). Mit 1,3-Butadien (R=H) erhält man das Kupplungsprodukt regio- und stereoselektiv.

Nickel-Catalyzed Dimerization and Carbosilylation of 1,3-Butadienes with Chlorosilanes and Grignard Reagents

Co-reporter:Jun Terao Dr.;Akihiro Oda;Aki Ikumi;Akifumi Nakamura;Hitoshi Kuniyasu Dr. Dr.

Angewandte Chemie International Edition 2003 Volume 42(Issue 29) pp:

Publication Date(Web):24 JUL 2003

DOI:10.1002/anie.200351579

In a multicomponent coupling reaction, 1,3-butadienes underwent Ni-catalyzed dimerization and carbosilylation in the presence of a chlorosilane and a Grignard reagent at −20 °C (see scheme). The coupling product was obtained regio- and stereoselectively when unsubstituted 1,3-butadiene was used. (R=H, Me, or C₉H₁₉; R′, R′′=hydrocarbon substituent.)

Copper-catalyzed coupling reaction of unactivated secondary alkyl iodides with alkyl Grignard reagents in the presence of 1,3-butadiene as an effective additive

Co-reporter:Ruwei Shen, Takanori Iwasaki, Jun Terao and Nobuaki Kambe

Chemical Communications 2012 - vol. 48(Issue 74) pp:NaN9315-9315

Publication Date(Web):2012/08/13

DOI:10.1039/C2CC34847K

Ni-catalyzed regioselective three-component coupling of alkyl halides, arylalkynes, or enynes with R–M (M = MgX′, ZnX′)

Co-reporter:Jun Terao, Fumiaki Bando and Nobuaki Kambe

Chemical Communications 2009(Issue 47) pp:NaN7338-7338

Publication Date(Web):2009/10/13

DOI:10.1039/B918548H

Synthesis of imidazo and benzimidazo[2,1-a]isoquinolines by rhodium-catalyzed intramolecular double C–H bond activation

Co-reporter:Vutukuri Prakash Reddy, Takanori Iwasaki and Nobuaki Kambe

Organic & Biomolecular Chemistry 2013 - vol. 11(Issue 14) pp:NaN2253-2253

Publication Date(Web):2013/02/28

DOI:10.1039/C3OB27396B

Pd-catalyzed cross-coupling reactions of alkyl halides

Co-reporter:Nobuaki Kambe, Takanori Iwasaki and Jun Terao

Chemical Society Reviews 2011 - vol. 40(Issue 10) pp:NaN4947-4947

Publication Date(Web):2011/07/25

DOI:10.1039/C1CS15129K

Conversion of a (sp3)C–F bond of alkyl fluorides to (sp3)C–X (X = Cl, C, H, O, S, Se, Te, N) bonds using organoaluminium reagents

Co-reporter:Jun Terao, Shameem Ara Begum, Yoshiaki Shinohara, Masahiro Tomita, Yoshitaka Naitoh and Nobuaki Kambe

Chemical Communications 2007(Issue 8) pp:NaN857-857

Publication Date(Web):2006/11/23

DOI:10.1039/B613641A

Cross-coupling of alkyl halides with Grignard reagents using nickel and palladium complexes bearing η3-allyl ligand as catalysts

Co-reporter:Jun Terao, Yoshitaka Naitoh, Hitoshi Kuniyasu and Nobuaki Kambe

Chemical Communications 2007(Issue 8) pp:NaN827-827

Publication Date(Web):2006/11/21

DOI:10.1039/B612586G

The cross-coupling of Grignard reagents with alkyl bromides and tosylates has been achieved by the use of η3-allylnickel and η3-allylpalladium complexes as catalysts.

Nickel-catalyzed synthesis of diarylsulfides and sulfones via C–H bond functionalization of arylamides

Co-reporter:Vutukuri Prakash Reddy, Renhua Qiu, Takanori Iwasaki and Nobuaki Kambe

Organic & Biomolecular Chemistry 2015 - vol. 13(Issue 24) pp:NaN6813-6813

Publication Date(Web):2015/05/13

DOI:10.1039/C5OB00149H

Titanocene-catalyzed alkylative dimerization of vinyl Grignard reagent using alkyl halides

Co-reporter:Yuuki Fujii, Jun Terao, Yuichiro Kato and Nobuaki Kambe

Chemical Communications 2008(Issue 44) pp:NaN5838-5838

Publication Date(Web):2008/10/06

DOI:10.1039/B813596G

Dimerization of vinyl Grignard reagents and concomitant alkylation with alkyl halides have been achieved by using Cp2TiCl2 as a catalyst.

Silver-catalyzed carbomagnesiation of terminal aryl and silylalkynes and enynes in the presence of 1,2-dibromoethane

Co-reporter:Yuuki Fujii, Jun Terao and Nobuaki Kambe

Chemical Communications 2009(Issue 9) pp:NaN1117-1117

Publication Date(Web):2009/01/07

DOI:10.1039/B820521C

Regioselective carbomagnesiation of terminal alkynes and enynes with alkylGrignard reagents has been achieved by the combined use of a silver catalyst and 1,2-dibromoethane.

Non-catalytic conversion of C–F bonds of benzotrifluorides to C–C bonds using organoaluminium reagents

Co-reporter:Jun Terao, Misaki Nakamura and Nobuaki Kambe

Chemical Communications 2009(Issue 40) pp:NaN6013-6013

Publication Date(Web):2009/09/22

DOI:10.1039/B915620H

A facile method for the conversion of C–F bonds of benzotrifluorides to C–C bonds has been developed using aluminium reagents in the absence of catalysts.

Cu-catalyzed regioselective carbomagnesiation of dienes and enynes with sec- and tert-alkyl Grignard reagents

Co-reporter:Hirohisa Todo, Jun Terao, Hideyuki Watanabe, Hitoshi Kuniyasu and Nobuaki Kambe

Chemical Communications 2008(Issue 11) pp:

Publication Date(Web):

DOI:10.1039/B716678H