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京都市西京区京都大学桂

京都大学大学院工学研究科

物質エネルギー化学専攻

触媒有機化学分野

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論文

Last Update 05.27.2016

73.

"Synthesis of Highly Insulated Conjugated Metallopolymers Containing Terpyridine−Metal Complexes"
Takuro Hosomi, Hiroshi Masai, Wakana Matsuda, Shu Seki, Tetsuaki Fujihara, Yasushi Tsuji, Jun Terao*
Chem. Lett., 2016, , in press.

Kyoto Univ.

A bridging monomer with terpyridine moieties on both ends of the insulated conjugated chain was successfully synthesized. The synthesis necessitated a new synthetic strategy, in which FeII was employed as a removable water-solubilizing substituent. The monomer was able to coordinate with FeII, CoII, NiII, or RuII to give highly insulated conjugated metallopolymers.

72.

"Carboxyzincation Employing Carbon Dioxide and Zinc Powder: Cobalt-Catalyzed Multicomponent Coupling Reactions with Alkynes"
Keisuke Nogi, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2016, 138, 5547-5550. DOI:10.1021/jacs.6b02961

Nogi

Cobalt-catalyzed carboxyzincation reactions employing carbon dioxide and zinc metal powder are developed. By using alkynes as substrates, regio- and stereodefined (Z)-β-zincated acrylates are provided. The corresponding alkenylzinc moiety can be converted to various substituents, affording multisubstituted acrylic acids. Furthermore, by adding electron-deficient alkene to the reaction system, the four-component coupling reactions of alkyne, alkene, CO2, and the Zn atom proceed via carboxyzincation.

71.

"Rational Design for Rotaxane Synthesis via Intramolecular Slippage: Control of Activation Energy by Rigid Axle Length"
Hiroshi Masai, Jun Terao*, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Eur. J., 2016, 22, 6624-6630. DOI:10.1002/chem.201600429

Kyoto Univ.

We describe a new concept for rotaxane synthesis through intramolecular slippage using π-conjugated molecules as rigid axles linked with organic soluble and flexible permethylated α-cyclodextrins (PM α-CDs) as macrocycles. Through hydrophilic?hydrophobic interactions and flipping of PM α-CDs, successful quantitative conversion into rotaxanes was achieved without covalent bond formation. The rotaxanes had high activation barrier for their de-threading, so that they were kinetically isolated and derivatized even under conditions unfavorable for maintaining the rotaxane structures. 1H?NMR spectroscopy experiments clearly revealed that the restricted motion of the linked macrocycle with the rigid axle made it possible to control the kinetic stability by adjusting the length of the rigid axle in the precursor structure rather than the steric bulkiness of the stopper unit.

70.

"Cobalt- and Nickel-Catalyzed Carboxylation of Alkenyl and Sterically Hindered Aryl Triflates Utilizing CO2"
Keisuke Nogi, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
J. Org. Chem., 2015, 80, 11618-11623. DOI:10.1021/acs.joc.5b02307

Nogi

A highly selective carbon-carbon bond-forming transformation of carbon dioxide (CO2) to the alcohol oxidation level has been disclosed. By employing a copper/bisphosphine catalyst system and hydrosilanes as the mild and easy-to-handle reducing agents, various allenes react with CO2 to give homoallylic alcohols regioselectively.

69.

"N-Heterocyclic Carbene Ligands Bearing Poly(ethylene glycol) Chains: Effect of the Chain Length on Palladium-catalyzed Coupling Reactions Employing Aryl Chlorides"
Tetsuaki Fujihara*, Takahiro Yoshikawa, Motoi Satou, Hidetoshi Ohta, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2015, 51, 17382-17385. DOI:10.1039/C5CC07588B

YoshikawaSatou

N-Heterocyclic carbenes bearing poly(ethylene glycol) chains of different length have been designed and employed as a ligand in palladium-catalyzed coupling reactions. The catalyst system having longer chains was found to be highly efficient for Suzuki-Miyaura coupling and borylation reactions employing aryl chlorides under mild reaction conditions.

68.

"Synthesis of Molecular Wires Strapped by π-Conjugated Side Chains: Integration of Dehydrobenzo[20]annulene Units"
Jun Terao*, Masami Ohsawa, Hiroshi Masai, Yuki Kurashige, Tetsuaki Fujihara, Yasushi Tsuji
J. Org. Chem., 2015, 80, 8874-8880. DOI:10.1021/acs.joc.5b01414

Kyoto Univ.

A highly selective carbon-carbon bond-forming transformation of carbon dioxide (CO2) to the alcohol oxidation level has been disclosed. By employing a copper/bisphosphine catalyst system and hydrosilanes as the mild and easy-to-handle reducing agents, various allenes react with CO2 to give homoallylic alcohols regioselectively.

67.

"Copper-catalyzed C-C bond-forming transformation of CO2 to the alcohol oxidation level: selective synthesis of homoallylic alcohols from allenes, CO2, and hydrosilanes"
Yosuke Tani, Kazunari Kuga, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2015, 51,13020-13023. DOI:10.1039/C5CC03932K

Dr. TaniKuga

A highly selective carbon-carbon bond-forming transformation of carbon dioxide (CO2) to the alcohol oxidation level has been disclosed. By employing a copper/bisphosphine catalyst system and hydrosilanes as the mild and easy-to-handle reducing agents, various allenes react with CO2 to give homoallylic alcohols regioselectively.

66.

"Palladium-catalyzed formal hydroacylation of allenes employing carboxylic anhydrides and hydrosilanes"
Tetsuaki Fujihara*, Takuro Hosomi, Cong Cong, Tomoya Hosoki, Jun Terao, Yasushi Tsuji*
Tetrahedron, 2015, 71, 4570-4574. DOI:

HosomiCongHosoki

The formal hydroacylation reaction of allenes has been developed employing carboxylic anhydrides as acyl sources and hydrosilanes as reducing reagents in the presence of a commercially available palladium complex as a catalyst. The reaction affords , -unsaturated ketones regio- and stereoselectively. The similar catalyst system is also effective for the reduction of carboxylic anhydrides to the corresponding aldehydes employing hydrosilanes.

65.

"Copper-Catalyzed Silylative Allylation of Ketones and Aldehydes Employing Allenes and Silylboranes"
Yosuke Tani, Tatsuya Yamaguchi, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
Chem. Lett., 2015, 44, 271-273. DOI:10.1246/cl.141018

TaniYamaguchi

The copper-catalyzed silylative allylation of ketones with allenes and silylboranes via an in-situ generated beta-silyl allylcopper intermediate has been developed. Various ketones and allenes were converted to the homoallylic tertiary alcohols bearing internal (E)-vinylsilane moieties regio- and stereoselectively in good to high yields. Aldehydes were also employed as electrophiles in the reaction.

64.

"Copper-Catalyzed Regiodivergent Silacarboxylation of Allenes with Carbon Dioxide and a Silylborane"
Yosuke Tani, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2015, 137, 4960-4963. DOI:10.1021/ol502538r

Tani

The regiodivergent silacarboxylation of allenes is developed under carbon dioxide atmosphere with PhMe2Si-B(pin) as a silicon source in the presence of a copper catalyst at 70 °C. The regioselectivity of the reaction is successfully reversed by the proper choice of ligand; carbox-ylated vinylsilanes are obtained with rac-Me-DuPhos as the ligand, whereas carboxylated allylsilanes are provided by employing PCy3. Thus, two different carboxylated silanes can be selectively and re-giodivergently synthesized from a single allene substrate.

63.

"Enhancement of Phosphorescence and Unimolecular Behavior in the Solid State by Perfect Insulation of Platinum-Acetylide Polymers"
Hiroshi Masai, Jun Terao*, Satoshi Makuta, Yasuhiro Tachibana, Tetsuaki Fujihara, Yasushi Tsuji
J. Am. Chem. Soc., 2014, 136, 14714-14717. DOI:10.1021/ja508636z

Kyoto Univ.

We demonstrate enhanced phosphorescence control through a systematic investigation of cyclodextrin-based insulated platinum. acetylide polymers with well-defined coverage areas.

62.

"Synthesis of an organic-soluble π-conjugated [3]rotaxane via rotation of glucopyranose units in permethylated β-cyclodextrin"
Jun Terao*, Yohei Konoshima, Akitoshi Matono, Hiroshi Masai, Tetsuaki Fujihara, Yasushi Tsuji
Beilstein J. Org. Chem., 2014, 10, 2800-2808. DOI:10.3762/bjoc.10.297

Kyoto Univ.

We synthesized symmetrically insulated oligo(para-phenylene) and oligothiophene with a pseudo-linked [3]rotaxane structure by full rotation of glucopyranose units via a flipping (tumbling) mechanism in the π-conjugated guest having two permethylated β-cyclodextrin units at both ends. We also succeeded in the synthesis of an organic-soluble fixed [3]rotaxane by a cross-coupling or complexation reaction of thus formed pseudo linked [3]rotaxane. Oligo(para-phenylene), oligothiophene, and porphyrin derivatives were used as π-conjugated guests with stopper groups.

61.

"Nickel-Catalyzed Double Carboxylation of Alkynes Employing Carbon Dioxide"
Tetsuaki Fujihara, Yuichiro Horimoto, Taiga Mizoe, Freed Bhasha Sayyed, Yosuke Tani, Jun Terao, Yasushi Tsuji*
Org. Lett., 2014, 16, 4960-4963. DOI:10.1021/ol502538r

HorimotoMizoe

The nickel-catalyzed double carboxylation of internal alkynes employing carbon dioxide (CO2) has been developed. The reactions proceed under CO2 (1 atm) at room temperature in the presence of a nickel catalyst, Zn powder as a reducing reagent, and MgBr2 as an indispensable additive. Various internal alkynes could be converted to the corresponding maleic anhydrides in good to high yields. DFT calculations disclosed the indispensable role of MgBr2 in the second CO2 insertion.

60.

"Cobalt-Catalyzed Carboxylation of Propargyl Acetates with Carbon Dioxide "
Keisuke Nogi, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2014, in press. DOI:10.1039/C4CC03644A

Nogi

The cobalt-catalyzed carboxylation of propargyl acetates with CO2 (1 atm) is described. The reaction proceeds at room temperature with Mn powder as a reducing reagent. Various propargyl acetates are converted to the corresponding carboxylic acids in good to high yields.

59.

"Copper-Catalyzed Borylative AllylAllyl Coupling Reaction"
Kazuhiko Semba, Naoto Bessho, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2014, 53, 9007-9011. DOI:10.1002/anie.201404173

Dr. SembaBessho

Borylative allyl-allyl coupling using allenes, bis(pinacolato)diboron, and allyl phosphates has been developed in the presence of a copper catalyst bearing an N-heterocyclic carbene ligand. The reaction affords boryl-substituted 1,5-diene derivatives in good to high yields with high regio- and (Z)-selectivity.

58.

"Palladium-Catalyzed Formal Arylacylation of Allenes Employing Acid Chlorides and Arylboronic Acids"
Kenta Tatsumi, Tetsuaki Fujihara*, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2014, 508476-8479. DOI:10.1039/C4CC03173C

Tatsumi

Palladium-catalyzed formal arylacylation of allenes using acid chlorides and arylboronic acids has been achieved. The reaction afforded the corresponding alpha,beta-unsaturated ketones regio- and stereoselectively.



57.

"Encapsulation by Cyclic Porphyrin Dimers using Various Interaction Modes"
Jun Terao,* Yusuke Chiba, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Lett., 2014, 43, 1374-1376. DOI:10.1246/cl.140391

Kyoto Univ.

We synthesized cyclic host molecules A, B, and C based on a rigid π-conjugated system composed of porphyrin and fluorene units. After transforming the ester units of a cyclic host B to carboxylates, the host C became soluble in water. These host molecules could encapsulate different molecules based on various interactions: coordination bonds between porphyrin-bound metals (Zn) and N atoms, π--π interactions, or hydrophobic interactions.

56.

"Synthesis and Redox Response of Insulated Molecular Wire Elongated through Iron-Terpyridine Coordination Bonds"
Jun Terao,* Takuro Hosomi, Hiroshi Masai, Wakana Matsuda, Shu Seki, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Lett., 2014, 43, 1289-1291. DOI:10.1246/cl.140365  

Kyoto Univ.

We synthesized an insulated bridging ligand consisting of a π-conjugated backbone sheathed by permethylated α-cyclodextrin and terpyridyl moieties at either end. This bridging ligand was able to coordinate with Fe2+ to afford an insulated metallopolymer that was elongated through coordination bonds. The molecular wire exhibited a reversible response to a chemical redox stimulus.

55.

"Molecular Wiring Method Based on Polymerization or Co-polymerization of an Insulated π-Conjugated Monomer"
Jun Terao,* Kyohei Homma, Yohei Konoshima, Masateru Taniguchi,* Manabu Kiguchi,* Yuuki, Komoto, Masayo Horikawa, Yasuhisa Naito, Tetsuaki Fujihara, Yasushi Tsuji
Bull. Chem. Soc. Jpn., 2014, 87, 871-873. DOI:10.1246/bcsj.20140082

Kyoto Univ.

A new type of molecular wiring method was developed based on the polymerisation or co-polymerization of an insulated π-conjugated monomer between nanosized electrodes.


54.

"Iron Oxide Catalyzed Reduction of Acid Chlorides to Aldehydes with Hydrosilanes"
Cong Cong, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Catal. Commun., 2014, 50, 25-28. DOI:10.1016/j.catcom.2014.02.018

Cong

Iron-catalyzed reduction of acid chlorides to the corresponding aldehydeswith a hydrosilane as a reducing agent has been developed. A simple mixture of a commercially available iron oxide (FeO) and tris(2,4,6-trimethoxyphenyl) phosphine (TMPP) as a catalyst realized the reduction of acid chlorides to the corresponding aldehydes under mild reaction conditions.

53.

"Synthesis of One-Dimensional Metal-Containing Insulated Molecular Wire with Versatile Properties Directed toward Molecular Electronics Materials"
Hiroshi Masai, Jun Terao,* Shu Seki, Shigeto Nakashima, Manabu Kiguchi, Kento Okoshi, Tetsuaki Fujihara, Yasushi Tsuji
J. Am. Chem. Soc., 2014, 164, 1742-1745. DOI:10.1021/ja411665k

Kyoto Univ.

We report, herein, the design, synthesis, and properties of new materials directed toward molecular electronics. A transition metal-containing insulated molecular wire was synthesized through the coordination polymerization of a Ru(II) porphyrin with an insulated bridging ligand of well-defined structure. The wire displayed not only high linearity and rigidity, but also high intramolecular charge mobility. Owing to the unique properties of the coordination bond, the interconversion between the monomer and polymer states was realized under a carbon monoxide atmosphere or UV irradiation. The results demonstrated a high potential of the metalcontaining insulated molecular wire for applications in molecular electronics.

52.

"Synthesis of Functionalized Insulated Molecular Wires by Polymerization of an Insulated π-Conjugated Monomer"
Jun Terao,* Kyohei Homma, Yohei Konoshima, Rika Imoto, Hiroshi Masai, Wakana Matsuda, Shu Seki, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Commun., 2014, 50, 658-660. DOI:10.1039/C3CC47105E

Kyoto Univ.

A new method for the synthesis of an insulated p-conjugatedmonomer was developed via the sequential self-inclusion followed by the elongation of the p-conjugated unit. The monomer was utilized in the synthesis of stimuli-responsive insulated molecular wires.

51.

"Synthesis and Characterization of Ruthenium(II) Complexes with Dendritic N-Heterocyclic Carbene Ligands"
Tetsuaki Fujihara, Takeru Nishida, Jun Terao, Yasushi Tsuji*
Inorg. Chim. Acta, 2014, 409, 174-178. DOI:10.1016/j.ica.2013.05.026

Nishida

Ru(II) complexes with a N-heterocyclic carbene ligand bearing flexible zeroth-, first-, or second-generation dendritic moieties were synthesized and characterized. The structure of the ruthenium complex with the zeroth-generation dendritic moieties was determined by X-ray crystallography. ONIOM calculations showed that the second generation dendritic moieties surrounded the ruthenium core. These complexes worked as active catalysts for the ring-closing metathesis at 25 oC.

50.

"Copper-Catalyzed Borylation of alpha-Alkoxyallenes with Bis(pinacolato)diboron: Efficient Synthesis of 2-Boryl-1,3-butadienes"
Kazuhiko Semba, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2013, 52, 12400-12403. DOI:10.1002/anie.201306843k
Highlighted in SYNFACT

Dr. Semba

2-Boryl 1,3-butadienes with various substitution patterns were formed in good to high yields in a copper-catalyzed borylation of aipha-alkoxy allenes with bis(pinacolato)diboron. The products were found to be useful intermediates for the synthesis of cyclic vinyl boranes, a,b-unsaturated ketones, and functionalized multisubstituted dienes.

49.

"Palladium-Catalyzed Reduction of Carboxylic Acids to Aldehydes with Hydrosilanes in the Presence of Pivalic Anhydride"
Tetsuaki Fujihara, Cong Cong, Jun Terao, Yasushi Tsuji*
Adv. Synth. Catal., 2013, 355, 3420-3424. DOI:10.1002/adsc.201300978
Highlighted in Back Cover Picture

Cong

A palladium catalyst system that allows the reduction of carboxylic acids to the corresponding aldehydes with hydrosilanes as reducing agent and pivalic anhydride as an indispensable reagent has been developed. A simple mixture of commercially available palladium complex Pd(dba)2, tri(p-tolyl)phosphane and methylphenylsilane realized the reduction of various aliphatic carboxylic acids as well as benzoic acids to aldehydes in good to high yields.

48.

"Palladium-Catalyzed Formal Hydroacylation of Allenes Employing Acid Chlorides and Hydrosilanes"
Tetsuaki Fujihara, Kenta Tatsumi, Jun Terao, Yasushi Tsuji*
Org. Lett., 2013, 15, 2286-2289. DOI:10.1021/ol400862k

Tatsumi

Palladium-catalyzed formal hydroacylation of allenes employing acid chlorides and hydrosilanes has been achieved. The reactions proceed with commercially available Pd(OAc)2 as a catalyst and HSi(iPr)3 as a reducing reagent, giving the corresponding alpha,beta-unsaturated ketones regio- and stereoselectively.

47.

"Design Principle for Increasing Charge Mobility of pai-Conjugated Polymers Using Regularly Localized Molecular Orbitals"
Jun Terao,* Akihisa Wadahama, Akitoshi Matono, Tomofumi Tada,* Satoshi Watanabe, Shu Seki,* Tetsuaki Fujihara, Yasushi Tsuji
Nature. Commun., 2013, 4, 1691. DOI:10.1038/ncomms2707

Kyoto Univ.

We demonstrate a new design principle for increasing the intramolecular charge mobility of pai-conjugated polymers by covering the pai-conjugated chain with macrocycles and regularly localizing pai-molecular orbitals to realize an ideal orbital alignment for charge hopping. Based on theoretical predictions, insulated wires containing meta-junctioned poly(phenylene-ethynylene) as the backbone units were designed and synthesized. The zigzag wires exhibited higher intramolecular charge mobility than the corresponding linear wires.

46.

"Copper-Catalyzed Highly Selective Hydroboration of Allenes and 1,3-Dienes"
Kazuhiko semba, Masataka Shinomiya, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Chem Eur. J., 2013, 19, 7125-7132 . DOI:10.1002/chem.201300443

Dr. Semba

Copper-catalyzed highly selective hydroboration of allenes was developed. Allylboranes and alkenylboranes were prepared selectively by choice of catalytic species (copper hydride and boryl copper). In addition, two types of alkenylboranes could be synthesized selectively by choice of appropriate ligand. The mechanistic studies clarified that the protonation of (Z)-sigma-allylcopper species was a key step for the present reactions.

45.

"Copper-Catalyzed Silacarboxylation of Internal Alkynes by Employing Carbon Dioxide and Silylboranes"
Tetsuaki Fujihara, Yosuke Tani, Kazuhiko semba, Jun Terao, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2012, 51, 11487-11490. DOI:10.1002/anie.201207148

Tani

The copper-catalyzed silacarboxylation of internal alkynes by employing silylboranes as the silicone source under an atmospheric pressure of carbon dioxide has been achieved. The reaction afforded silalactones in good to high yields. In addition, we demonstrated that the silalactone were good substrates for the Hiyama cross-coupling reaction.

44.

"Palladium-Catalyzed Reduction of Acid Chlorides to Aldehydes with Hydrosilanes"
Tetsuaki Fujihara, Cong Cong, Tomohiro Iwai, Jun Terao, Yasushi Tsuji*
Synlett, 2012, 23, 2389-2392. DOI:10.1055/s-0032-1317155

Cong

An efficient synthesis of aldehydes from acid chlorides with hydrosilanes as a reducing agent in the presence of a palladium catalyst has been achieved. A simple mixture of commercially available Pd(dba)2 and P(Mes)3 as a catalyst realized the reduction of various acid chlorides including aliphatic acid chlorides and a, -unsaturated acid chlorides to the corresponding aldehydes in good to high yields under mild reaction conditions.

43.

"Palladium-Catalyzed Esterification of Aryl Halides Using Aryl Formates without the Use of External Carbon Monoxide"
Tetsuaki Fujihara, Tomoya Hosoki, Yuko Katafuchi, Tomohiro Iwai, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2012, 48, 8012-8014. DOI:10.1039/C2CC33944G

Hosoki

Aryl formates are efficient carbon monoxide sources in palladium-catalyzed esterification of aryl halides. The carbonylation readily proceeds at ambient pressure without the use of external carbon monoxide to afford the corresponding esters in high yields. During the reaction aryl formates were converted to carbon monoxide and the corresponding phenols by the aid of a base.

42.

"Nickel-Catalyzed Carboxylation of Aryl and Vinyl Chlorides Employing Carbon Dioxide"
Tetsuaki Fujihara, Keisuke Nogi, Tinghua Xu, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2012, 134, 9106-9109. DOI:10.1021/ja303514b

Nogi

The nickel-catalyzed carboxylation of aryl and vinyl chlorides employing carbon dioxide (CO2) has been developed. The reactions proceeded under a CO2 pressure of 1 atm at room temperature in the presence of nickel catalysts and Mn powder as a reducing agent. Various aryl chlorides could be converted to the corresponding carboxylic acid in good to high yields. Furthermore, vinyl chlorides were successfully carboxylated with CO2. Mechanistic study suggests that Ni(I) species is involved in the catalytic cycle.

41.

"Synthesis of Insulated Pt-alkynyl Complex Polymer"
Jun Terao,* Hiroshi Masai, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Lett., 2012, 41, 652-653. DOI:10.1246/cl.2012.652

Kyoto Univ.

A Pt-alkynyl polymer in which the -conjugated chain was completely covered with macrocycles was synthesized by intramolecular self-inclusion of an oligomeric phenylene ethynylene as a guest moiety with two permethylated -cyclodextrins as hosts followed by copolymerization with a Pt(II) complex.

40.

"Copper-Catalyzed Highly Selective Semihydrogenation of Nonpolr Carbon-Carbon Multiple Bonds Using a Silane and an Alcohol"
Kazuhiko Semba, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Adv. Synth. Catal., 2012, 354, 1542-1550. DOI:10.1246/cl.2012.652

Semba

A copper catalyst bearing a suitable Xantphos derivative or NHC ligand was found to be highly efficient for selective semihydrogenation of nonpolar unsaturated compounds using a mixture of a silane and an alcohol as a reducing agent. The catalytic system was useful for selective semihydrogenation of internal alkynes to (Z)-alkenes with suppressing overreduction to the corresponding alkanes.

39.

"Copper-Catalyzed Highly Regio- and Stereoselective Directed Hydroboration of Unsymmetrical Internal Alkynes: Controlling Regioselectivity by Choice of Catalytic Species"
Kazuhiko Semba, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Chem. Eur. J., 2012, 18, 4179-4184. DOI:10.1002/chem.201103612

Semba

We have developed a copper-catalyzed highly regio- and stereoselective hydroboration of unsymmetrical internal alkynes. The regioselectivity is controllable by using one of two different catalytic species (LCu-H and LCu-B) generated from borylation reagents HBpin and B2pin2, respectively.

38.

"Iridium-Catalyzed Addition of Aroyl Chlorides and Aliphatic Acid Chlorides to Terminal Alkynes"
Tomohiro Iwai, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2012, 134, 1268-1274. DOI:10.1021/ja209679c

Dr. Iwai

Iridium complexes show high catalytic activity in intermolecular additions of acid chlorides to terminal alkynes to afford valuable (Z)-β-chloro-α,β-unsaturated ketones. Ligands in the catalytic system play a crucial role in this reaction. An N-heterocyclic carbene (NHC) is an efficient ligand for the addition of aroyl chlorides, while dicyclohexyl(2-methylphenyl)phosphine (PCy2(o-Tol)) is indispensable for the reaction of aliphatic acid chlorides. The addition reactions proceed regio- and stereoselectively with suppression of decarbonylation and β-hydrogen elimination.

37.

"Synthesis of insulated molecular wire by click polymerization"
Jun Terao,* Kazuya Kimura, Shu Seki, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Commun., 2011, 47, 1577-1579. DOI:10.1039/c1cc13115j

Kyoto Univ.

We developed a new method for the synthesis of an organic-soluble insulated molecular wire (IMW) with permethylated cyclodextrin (PMCD); this method involves click polymerization of linked [2]rotaxane (pseudo[1]rotaxane) containing azide and alkynyl groups at both ends of a pai-conjugated guest.

36.

"Ruthenium-catalyzed ring-closing metathesis accelerated by long-range steric effect"
Tetsuaki Fujihara, Yoshikazu Tomike, Toshiyuki Ohtake, Jun Terao, Yasushi Tsuji*
Chem. Commun., 2011, 47, 9699-9701. DOI:10.1039/C1CC13304G

tomikeohtake

Ruthenium-based metathesis catalysts with a N-heterocyclic carbene ligand bearing 2,3,4,5-tetraphenylphenyl moieties (1-TPPh and 1-TPPh*) are developed. The highly active catalyst system has been realized in THF by the combination of 1-TPPh* and CuCl as a phosphine scavenger.

35.

"Synthesis of Head-to-tail-type Cyclodextrin-based Insulated Molecular Wire"
Jun Terao,* kazuhiro Ikai, Nobuaki Kambe, Shu Seki, Akinori Saeki, Kento Okoshi, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Commun., 2012, 48, 6816-6818. DOI:10.1039/c1cc13012a

Kyoto Univ.

We developed a new method for synthesizing an organic-soluble insulated molecular wire (IMW) with permethylated cyclodextrin (PMCD). The IMW obtained using this method is highly soluble in a variety of organic solvents and has a high covering ratio, regioregularity, rigidity, photoluminescence efficiency, and interchain hole mobility.

34.

"Palladium(II) complexes bearing a salicylaldiminato ligand with a hydroxyl group: synthesis, structures, deprotonation, and catalysis"
Yusuke Murata, Hiroyuki Ohgi, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Inorg. Chim. Acta, 2011, 368, 237-241. DOI:10.1016/j.ica.2010.12.036

Murata

Palladium complexes with a salicylaldiminato ligand bearing a hydroxyl group have been synthesized and characterized. A reversible deprotonation/protonation of the hydroxyl moiety was observed, while such behaviour was impossible with a related palladium complex bearing a methoxyl group in place of the hydroxyl group. The deprotonation affected its catalytic behaviour.

33.

"Palladium-Catalyzed Hydroesterification of Alkynes Employing Aryl Formates without the Use of External Carbon Monoxide"
Yuko Katafuchi, Tetsuaki Fujihara, Tomohiro Iwai, Jun Terao, Yasushi Tsuji*
Adv. Synth. Catal., 2011, 353, 475-482. DOI:10.1002/adsc.201000750

Katafuchi

The hydroesterification of alkynes employing aryl formates occurred at ambient pressure in the presence of Pd-xantphos catalyst system to afford alpha,beta-unsaturated esters regio- and stereoselectively. The reaction can be carried out without the use of external carbon monoxide, and no directing group is required. During the reaction aryl formates were converted to carbon monoxide and the corresponding phenols.

32.

"Copper-Catalyzed Hydrocarboxylation of Alkynes Using Carbon Dioxide and Hydrosilanes"
Tetsuaki Fujihara, Tingua Xu, Kazuhiko Semba, Jun Terao, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2011,50, 523-527. DOI:10.1002/anie.201006292
Highlighted in Angew. Chem. (Angew. Chem. Int. Ed., 2011, 50, 6210.)

Xu

We have reported the copper-catalyzed hydrocarboxylation of alkynes using CO2. The use of mild and easy-to-handle hydrosilane as a reducing agent realizes highly efficient hydrocarboxylation of alkynes to afford alpha,beta-unsaturated carboxylic acids effectivery. An alkenyl-copper species generated by the reaciton of a copper hydride complex with an alkyne was found to be an important intermediate.

31.

"Iridium-Catalyzed Annulation of N-Arylcarbamoyl Chlorides with Internal Alkynes"
Tomohiro Iwai, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2010, 132, 9602-9603. DOI:10.1021/ja104153k

Iwai

An iridium complex successfully catalyzed the annulation of various N-arylcarbamoyl chlorides with internal alkynes to afford 2-quinolones in good to excellent yields. The present reaction is widely applicable to substrates with various functionalities. An amide-iridacycle complex was isolated, and it is likely that such an iridacycle species is a key intermediate in the catalytic reaction.

30.

"Synthesis of Linked Symmetrical [3]Rotaxane Having an Oligomeric Phenylene Ethynylene Unit as a pi-Guest via Double Sonogashira Cross-coupling"
Jun Terao,* Akihisa Wadahama, Tetsuaki Fujihara, Yasushi Tsuji
Chem. Lett., 2010, 39, 518-519. DOI:10.1246/cl.2010.518

Kyoto Univ.

Linked symmetric [3]rotaxanes consisting of an oligomeric phenyleneethynylene (OPE) unit as a 3-conjugated guest and two molecules of organic soluble permethylated alpha-cyclodextrins (PM alpha-CDs) as macrocyclic hosts have been synthesized by intramolecular self-inclusion of an OPE guest moiety carrying PM alpha-CDs followed by double cross-coupling reaction with 1,4- diiodobenzene under the Sonogashira coupling conditions.

29.

"Palladium-Catalyzed Intermolecular Addition of Formamides to Alkynes"
Tetsuaki Fujihara, Yuko Katafuchi, Tomohiro Iwai, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2010, 132, 2094-2098. DOI:10.1021/ja910038p
Highlighted in SYNFORM

Katafuchi

Novel palladium system for an intermolecular addition of formamides to alkynes has been developed. The reaction of formamides with internal alkynes in the presence of a palladium catalyst with acid chloride as an additive. The same catalyst system realized the first example of the addition of formamides to terminal alkynes. A hydridopalladium species would be formed as a key intermediate with in situ generated HCl under the reaction conditions.

28.

"Copper-Catalyzed Hydrosilylation with a Bowl-Shaped Phosphane Ligand: Preferential Reduction of a Bulky Ketone in the Presence of an Aldehyde"
Tetsuaki Fujihara, Kazuhiko Semba, Jun Terao, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2010, 49, 1472-1476. DOI:10.1002/anie.200906348

Semba

We have developed a highly active Cu catalyst with bowl-shaped phosphane (BSP) as a ligand in the hydrosilylation. The reactions are faster with more bulky ketones as substrates. Noteworthy is that the present catalysts realize unprecedented preferential reduction of a bulky ketone in the presence of an aldehyde without any protections.

27.

"Synthesis of Organic-Soluble Conjugated Polyrotaxanes by Polymerization of Linked Rotaxanes"
Jun Terao,* Susumu Tsuda, Yuji Tanaka, Kento Okoshi, Tetsuaki Fujihara, Yasushi Tsuji, Nobuaki Kambe*
J. Am. Chem. Soc., 2009, 131, 16004-16005. DOI:10.1021/ja9074437
Highlighted in SYNFACT

Kyoto Univ.

We have developed a new method for synthesizing polyrotaxanes (IMWs) through the polymerization of structurally defined rotaxane monomers. The IMWs thus formed have a high covering ratio, rigidity, and PL efficiency; further, they are readily soluble in a variety of organic solvents.

26.

"Synthesis and Structural Characterization of a Series of Mono-O-(diphenylphosphinobenzyl)calix[6]arenes with and without tert-Butyl Moieties at the Upper Rim"
Tetsuaki Fujihara, Sho Kubouchi, Yasushi Obora, Makoto Tokunaga, Kazuhiro Takenaka, Yasushi Tsuji*
Bull. Chem. Soc. Jpn., 2009, 82, 1183-1193. DOI:10.1246/bcsj.82.1187

Kubouchi

Synthesis and characterization of a series of mono-O-(diphenylphosphinobenzyl)calix[6]arenes are presented. The two types of calix[6]arene moieties with tert-butyl groups at the upper rim and without the tert-butyl groups were used. With regard to the position of a phosphorus atom, the diphenylphosphino group was introduced onto the ortho, meta, or para positions with the benzyl ether moiety. These phosphines as well as their oxides were fully characterized by elemental analysis, NMR measurements, and HR-ESI-MS. These phosphines were found to be good ligands in the Rh-catalyzed hydroformylation.

25.

"Iridium-Catalyzed Addition of Acid Chlorides to Terminal Alkynes"
Tomohiro Iwai, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
J. Am. Chem. Soc., 2009, 131, 6668-6669. DOI:10.1021/ja901778y
Highlighted in JACS-Beta (J. Am. Chem. Soc., 2009, 131, 15075-15077.)
Highlighted in Angew. Chem. (Angew. Chem. Int. Ed., 2009, 48, 9592-9594.)
Highlighted in SYNFACT

Iwai

An iridium N-heterocyclic carbene (NHC) complex, IrCl(cod)(IPr), successfully catalyzed an addition of common aromatic acid chlorides to terminal alkynes to afford (Z)-b-chloro-a,b-unsaturated ketones regio- and stereoselectively. Theis reaction can be applied to a catalytic synthesis of furans. By using a phosphine (RuPhos) as the ligand, the addition occurred with the decarbonylation to give the corresponding (Z)-vinyl chlorides.

24.

"A Triarylphosphine Ligand Bearing Dodeca(ethylene glycol) Chains: Enhanced Efficiency in the Palladium-catalyzed Suzuki-Miyaura Coupling Reaction"
Tetsuaki Fujihara, Shohei Yoshida, Jun Terao, Yasushi Tsuji*
Org. Lett., 2009, 11, 2121-2124. DOI:10.1246/cl.2012.652
Highlighted in SYNFACT

Yoshida

A new phosphine bearing dodeca(ethylene glycol) chains has been synthesized and employed as a ligand in the palladium-catalyzed Suzuki-Miyaura coupling reaction. The system was found to be highly effective using unactivated aryl chlorides as the substrate.

23.

"Iridium-catalyzed Decarbonylation of Aldehydes under Mild Conditions"
Tomohiro Iwai, Tetsuaki Fujihara, Yasushi Tsuji*
Chem. Commun., 2008, 6215-6217. DOI:10.1039/b813171f

Iwai

The catalytic decarbonylation of aldehydes was developed by using commercially available [IrCl(cod)]2 and PPh3 under mild conditions, and the method could be widely applicable to various substrates with different functionalities.

22.

"Triarylphosphanes with Dendritically Arranged Tetraethylene Glycol Moieties at the Periphery: an Efficient Ligand for the Palladium-Catalyzed Suzuki-Miyaura Coupling Reaction"
Tetsuaki Fujihara, Shohei Yoshida, Hidetoshi Ohta, Yasushi Tsuji*
Angew. Chem. Int. Ed., 2008, 47, 8310-8314. DOI:10.1021/ol900578g

Yoshida

New phosphanes having the tetraethylene glycol (TEG) or n-C12 moieties introduced dendrically at the periphery were designed and prepared. Among them, the higher dendritic phosphane bearing the TEG moiety is particularly effective as a ligand in the palladium-catalyzed Suzuki-Miyaura coupling reaction.

21.

"N-Heterocyclic Carbene Ligands Bearing Hydrophilic and/or Hydrophobic Chains: Rh(I) and Pd(II) Complexes and Their Catalytic Activity"(Front Cover)
Hidetoshi Ohta, Tetsuaki Fujihara, Yasushi Tsuji*
Dalton Trans., 2008, 379-385. DOI:10.1039/b715412g

Ohta

A series of novel imidazolium salts bearing hydrophilic tetraethylene glycol (TEG) and/or hydrophobic long-chain alkyl (n-C12) functionalities, which were precursors for desired N-heterocyclic carbene (NHC) ligands, were synthesized and characterized. In the Suzuki-Miyaura coupling reaction with Pd(II) complexes with these NHC ligands, the TEG moiety enhances catalytic activity considerably.

20.

"Rhodium(III) Complexes with a Bidentate N-Heterocyclic Carbene Ligand Bearing Flexible Dendritic Frameworks"
Tetsuaki Fujihara, Yasushi Obora, Makoto Tokunaga, Yasushi Tsuji*
Dalton Trans., 2007, 1567-1569. DOI:10.1039/b701104k

CRC

Rh(III) complexes with a bidentate N-heterocyclic carbene ligand bearing flexible dendrimtic framworks have been synthesized and fully characterized by X-ray crystallographic analysis, NMR measurements and theoretical calculations.

19.

"A Bowl-Shaped Phosphine as a Ligand in Palladium-Catalyzed Suzuki-Miyaura Coupling of Aryl Chlorides: Effect of a Depth of the Bowl"
Hidetoshi Ohta, Makoto Tokunaga, Yasushi Obora, Tomohiro Iwai, Tetsuo Iwasawa, Tetsuaki Fujihara, Yasushi Tsuji*
Org. Lett., 2007, 9, 89-92. DOI:10.1021/ol0626138

Ohta

Bowl-shaped phosphine ligands were found to be highly effective in the palladium-catalyzed Suzuki-Miyaura coupling of unactivated aryl chlorides, in which the depth of the bowl affected the catalytic activity considerably.

18.

N-Heterocyclic Carbenes Bearing a 2,3,4,5-Tetraphenylphenyl and Its Higher Dendritic Frameworks"
Hiromichi Sato, Tetsuaki Fujihara, Yasushi Obora, Makoto Tokunaga, Junya Kiyosu, Yasushi Tsuji*
Chem. Commun.,2007, 269-271. DOI:10.1039/b612385f

CRC

Novel rhodium(I) complexes with N-heterocyclic carbenes bearing a 2,3,4,5-tetraphenylphenyl and its higher dendritic frameworks were synthesized and the complexes were used as catalysts in rhodium-catalyzed hydrosilylation of a,b-unsaturated ketones to show high 1,4-adduct selectivity.

17.

"Experimental and Theoretical Evaluation of Charge Distribution over Ruthenium and Dioxolene Framework of [Ru(OAc)(dioxolene)(trpy)] (trpy = 2,2':6',2"-terpyridine) depending on Substituents"
Tohru Wada, Masahiro Yamanaka, Tetsuaki Fujihara, Yuji Miyazato, Koji Tanaka*
Inorg. Chem., 2006, 45, 8887-8894. DOI:10.1021/ic060696i

IMS

A series of ruthenium complexes [Ru(OAc)(dioxolene)(terpy)] having various substituents on the dioxolene ligand (dioxolene) were prepared. The resonance between the Ru(II)-semiquinone and Ru(III)-catecholato frameworks shifts to the latter with an increase of the number of electron-withdrawing substituents on the dioxolene ligand. DFT calculations also support the increase of the Ru spin density Ru(III)-character with an increase of the number of Cl atoms on the dioxolene ligand. Electron-withdrawing groups decrease the energy levels of both the SOMO and LUMO. Successive shifts in the electronic structure between the RuII(sq) and RuIII(cat) frameworks caused by the variation of the substituents are compatible with the experimental data.

16.

"Phosphines Having a 2,3,4,5-Tetraphenylphenyl Moiety: Effective Ligands in Palladium-catalyzed Transformations of Aryl Chlorides"
Tetsuo Iwasawa, Tomoko Komano, Atsunori Tajima, Makoto Tokunaga, Yasushi Obora, Tetsuaki Fujihara, Yasushi Tsuji*
Organometallics, 2006, 25, 4665-4669. DOI:10.1021/om060615q

CRC

Three new triarylphosphines were prepared which have a 2,3,4,5-tetraphenylphenyl (TPPh) moiety on one of the phenyl rings (at ortho, meta, or para) of triphenylphosphine. Among them, the ortho derivative is particularly effective to utilize unactivated aryl chlorides in three different palladium catalyzed reactions.

15.

"Comparison of Basicity of Diimine and Quinoid Group of 1,10-Phenanthroline-5,6-dione Ligated on Pt(II)"
Rei Okamura, Tetsuaki Fujihara, Tohru Wada, Koji Tanaka*
Bull. Chem. Soc. Jpn., 2006, 79, 106-112. DOI:10.1246/bcsj.79.106

IMS

A platinum(II) complex bearing 1,10-phenanthroline-5,6-dione was newly prepared and characterized. An X-ray crystallographic study of the complex revealed that the ligand coordinates to platinum with the N,N'-chelate form. The basicity of the quinoid part of the ligand and of the diimine one was evaluated in the absence and the presence of Li ion by means of UV-vis spectroscopy and cyclic voltammetry.

14.

"Dendrimer N-Heterocyclic Carbene Complexes with Rhodium(I) at the Core"(Inside Front Cover)
Tetsuaki Fujihara, Yasushi Obora, Makoto Tokunaga, Hiromichi Sato, Yasushi Tsuji*
Chem. Commun., 2005, 4526-4528. DOI:10.1039/b506927k

CRC

Novel dendrimer N-heterocyclic carbene complexes with rhodium(I) located at the core were synthesized and the positive dendrimer effect was found in the hydrosilylation of ketones catalyzed by them.

13.

"Structural Characterization of Ruthenium.Dioxolene Complexes with RuII-SQ and RuIII-Cat Frameworks"
Tetsuaki Fujihara, Rei Okamura, Koji Tanaka*
Chem. Lett., 2005, 35,1562-1563. DOI:10.1246/cl.2005.1562

IMS

The structural and electronic properties of [RuII(trpy)(ClSQ)(PPh3)]+ and [RuII(trpy)(ClCat)(PPh3)] have been characterized by X-ray diffractometry, UV-vis spectroscopy, ESR and electrochemistry.

12.

"Redox Behavior of New Ru-Dioxolene-Ammine Complexes and Catalytic Activity toward Electrochemical Oxidation of Alcohol under Mild Conditions"
Takami Hino, Tohru Wada, Tetsuaki Fujihara, Koji Tanaka*
Chem. Lett., 2004, 35,1596-1597. DOI:10.1246/cl.2004.159

IMS

The new Ru-dioxolene-ammine complexes were prepared. They have an ability to oxidize MeOH and 2-PrOH catalytically under very mild conditions such as the electrolysis at 0V (vs SCE) in CH2Cl2.

11.

"Strong Interaction between Carbonyl and Dioxolene Ligands Caused by Charge Distribution of Ruthenium-dioxolene Frameworks of Mono- and Dicarbonylruthenium Complexes"(Selected Paper)
Tohru Wada, Tetsuaki Fujihara, Mizuno Tomori, Dai Ooyama, Koji Tanaka*
Bull. Chem. Soc. Jpn., 2004, 77,741-749. DOI:10.1246/bcsj.77.741

IMS

One-electron reduction of the monocarbonyl Ru(II)-semiquinone complexes caused a red shift of the CO bands in a range of 41 to 56 cm-1, which was substantially larger than those of carbonyl Ru(II)-polypyridyl complexes. Two CO bands of dicarbonyl Ru(II)-bis(semiquinone) complexes also shifted to lower wavelength in a range of 53 to 99 cm-1 upon two electron reduction of the complexes. The unusually large red shift of the CO bands upon reduction of carbonyl Ru(II)-dioxolene complexes compared with those of Ru(II)-polypyridyl complex is ascribed to a strong electronic interaction between carbonyl and dioxolene ligands.

10.

"Acid-base Equilibria of Various Oxidation States of Aqua-ruthenium Complexes with 1,10-Phenanthroline-5,6-dione in Aqueous Media"
Tetsuaki Fujihara,Tohru Wada, Koji Tanaka*
Dalton Trans., 2004, 3221-3226. DOI:10.1039/b312310c

IMS

Syntheses and pH dependent electrochemical properties of aqua-Ru complexes are presented. The proton dissociation constants of various oxidations state of the complexes were evaluated by simulation of E1/2 values of those redox potentials depending on pH. The redox behavior is reasonably explained by not only the similar successive metal-centered redox reactions but also simultaneous two-electron quinone/catechol redox couple of the ligand including the contribution of hydration on a carbonyl carbon.

9.

"Syntheses and Electrochemical Properties of Ruthenium(II) Complexes with 4,4'-Bipyrimidine and 4,4'-Bipyrimidinium ligands"
Tetsuaki Fujihara,Tohru Wada, Koji Tanaka*
Inorg. Chim. Acta, 2004, 357, 1205-1212. DOI:10.1016/j.ica.2003.10.015

IMS

The syntheses and electrochemical properties of novel Ru(II) polypyridyl complexes with 4,4'-bipyrimidine and with a quaternized 4,4'-bipyrimidinium ligand are presented. The The structural characterization revealed that the ligand coordinated to the ruthenium atom with the bidentate fashion. Diquaternization of the noncoordinating The electrochemical and spectroelectrochemical properties of the complexes are described.

8.

"Coordination Ability of 1,10-Phenanthroline-5,6-dione: Syntheses and Redox Behavior of a Ru(II) Complex with an o-Quinoid Moiety and of Bridged Ru(II)-M(II) Complexes (M = Pd, Pt)"
Tetsuaki Fujihara, Rei Okamura, Tohru Wada, Koji Tanaka*
Dalton Trans., 2003, 3221-3226. DOI:10.1039/b304912d

IMS

The synthesis and electrochemical properties of a Ru(II) complex having a redox active ligand, 1,10-phenanthroline- 5,6-dione and mixed-metal complexes with Pd(II) abd Pt(II) are presented. The quinoid moiety was endowed with coordination ability to metals by one- and two-electron reduction of the complex.

7.

"Synthesis and Properties of Rhodium(III) Porphyrin Cyclic Tetramer and Cofacial Dimer"
Keiko Fukushima, Kenji Funatsu, Akio Ichimura, Yoichi Sasaki, Masamitsu Suzuki, Tetsuaki Fujihara, Kiyoshi Tsuge, Taira Imamura*
Inorg. Chem., 2003, 42, 3187-3193. DOI:10.1021/ic020652j

Hokkaido Univ.

Rhodium(III) porphyrin tetramers were self-assembled and characterized by 1H NMR spectroscopy, infrared spectroscopy, and electron spray ionization-mass spectroscopy methods.

6.

"Synthesis, Properties and Crystal Structure of a Novel Anthracene-Bridged Mo-Zn Porphyrin Dimer"
Tetsuaki Fujihara, Kiyoshi Tsuge, Yoichi Sasaki, Yasuhiro Kaminaga, Taira Imamura*
Inorg. Chem., 2002, 41, 1170-1176. DOI:10.1021/ic010323b

Hokkaido Univ.

The synthesis and properties of a novel anthracene-bridged porphyrin dimer having an oxomolybdenum(V) porphyrin unit (DPA)[MoVO(OMe)][ZnII(MeOH)] were synthesized. The structure of the complex demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo ligand on the Mo(V) ion in the binding pocket of DPA.

5.

"Unusual Oxidation of Oxo-peroxomolybdenum(VI) Tetramesitylporphyrin Giving Molybdenum(V) Porphyrin and Dioxygen"
Tetsuaki Fujihara, Kazuhiro Myougan, Akio Ichimura, Yoichi Sasaki, Taira Imamura*
Chem. Lett., 2001, 178-179. DOI:10.1246/cl.2001.178

Hokkaido Univ.

The one-electron oxidation of MoVIO(tmp)(O2) gave a product with reduced metal ion, oxomolybdenum(V) tetramesitylporphyrin, by releasing O2. These were observed by UV-vis and electrochemical measurements.

4.

"Steric Effects of Porphyrin Rings on Dioxygenation: Synthesis and Kinetic Studies of Molybdenum Porphyrin Dioxygen Complexes with Naphthyl Groups"
Junichi Tachibana, Tetsuaki Fujihara, Yoichi Sasaki, Taira Imamura*
Inorg. React. Mech., 2000, 2, 85-91.

Hokkaido Univ.

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3.

"Reversibility in the Formation of Oxo(peroxo)porphyrinatomolybdenums"
Tetsuaki Fujihara, Koji Hoshiba, Yoichi Sasaki, Taira Imamura*
Bull. Chem. Soc. Jpn., 2000, 73, 383-390. DOI:10.1246/bcsj.73.383

Hokkaido Univ.

A series of oxo(peroxo)porphyrinato molybdenums(VI) including new dioxygen complexes were synthesized and characterized. The electro and steric conditons on the porphyrin rings afffected the dioxygenation reaction.

2.

"Solid and Solution State Structures of a Reversible Molecular Oxygen-Carrying Molybdenum Porphyrin Dioxygen Complex"
Tetsuaki Fujihara, Nicholas H. Rees, Keisuke Umakoshi, Junichi Tachibana, Yoichi Sasaki, William McFarlane, Taira Imamura*
Chem. Lett., 2000, 102-103. DOI:10.1246/cl.2000.102

Hokkaido Univ.

The molecular structure of a reversible oxygen carrier, MoVIO(tmp)(O2) has been characterized by X-ray crystallography. Oxo and dioxygen ligands are actually coordinated with cis conformation, which leads to a saddle-like distortion of the porphyrin ring. The result of 2D ROESY shows the distortion of the porphyrin ring is retained in solution.

1.

"Preparation of Molybdenum Porphyrin Dioxygen Complexes without Bulky Substituents"
Tetsuaki Fujihara, Yoichi Sasaki, Taira Imamura*
Chem. Lett., 1999, 403-404. DOI:10.1246/cl.1999.403

Hokkaido Univ.

Molybdenum porphyrin dioxygen complexes wtihout bulky substituents were successfully synthesized by the direct oxydation of the corresponding Mo(IV) complexes with oxygen in the solid state.

総説

Last Update 03.07.2015

11.

"Transition-Metal-Catalyzed Fixation of Carbon Dioxide via Carbon-Carbon Bond Formation" (Review)
Tetsuaki Fujihara, Yasushi Tsuji*
J. Jpn. Petrol. Inst., 2016, 59, 84-92. DOI:

Kyoto Univ.

Carbon dioxide (CO2) is a readily available and renewable chemical feedstock, but the thermodynamic characteristics of CO2 limit its widespread use in chemical reactions. This review summarizes the transformation of CO2 via carbon-carbon bond-forming reactions. Ni complexes catalyzed the carboxylation of less reactive aryl chlorides and double carboxylation of internal alkynes in the presence of suitable reducing agents such as Mn or Zn powders under 1 atm of CO2. Using Cu complexes as catalysts under CO2 atmosphere, hydrocarboxylation and silacarboxylation of alkynes proceeded efficiently using hydrosilanes and silylboranes, respectively, as the reagents.

10.

"Copper-catalyzed borylative transformations of non-polar carbon?carbon unsaturated compounds employing borylcopper as an active catalyst species" (Review)
Kazuhiko Semba, Tetsuaki Fujihara, Jun Terao, Yasushi Tsuji*
Tetrahedron, 2015, 71, 2183-2197. DOI:10.1039/C4CY00070F

Kyoto Univ.

Copper-catalyzed borylative transformations of non-polar carbon-carbon unsaturated compounds using borylcopper as an active catalyst species are described in this review. First, the importance of developing synthetic methods for preparation of organoboronic acids and their derivatives in modern organic synthesis is addressed and the background of this research area is briefly introduced. Subsequently, addition of the borylcopper species across carbon-carbon multiple bonds (borylcupration) is discussed by showing several examples of stoichiometric reactions of the borylcopper with alkenes, alkynes, and 1,2-dienes (allenes), since the borylcupration is the most important elemental step in the copper-catalyzed borylative transformations.

9.

"Regioselective Transformation of Alkynes Catalyzed by a Copper Hydride or Boryl Copper Species" (Rerspective)
Tetsuaki Fujihara, Kazuhiko Semba, Jun Terao, Yasushi Tsuji*
Catal. Sci. Technol., 2014, 4, 1699-1709. DOI:10.1039/C4CY00070F

Kyoto Univ.

This review summarizes the transformation of alkynes using a copper hydride (Cu-H) or boryl copper (Cu-B) species as the active species. The semihydrogenation, hydrocarboxylation, and hydroboration of alkynes have been developed using Cu-H as the active species. The hydroboration, diboration, carboboration and boracarboxylation of alkynes involve the Cu-B species. These transformations afforded multi-substituted alkenes that are potentially good intermediates in organic synthesis. The key to the regioselective transformation is the addition of the Cu-H or Cu-B species to an alkyne, to afford the corresponding alkenylcopper intermediate regioselectively.

8.

"Transiton Metal-Catalyzed Synthesis of π-Conjugated Cyclic Esters and Amides from Alkynes and Carbonyl Reagents" (Review)
Tetsuaki Fujihara, Yasushi Tsuji*
Heterocycles, 2014, 89, 1343-1367. DOI:10.3987/REV-13-786

Kyoto Univ.

The transition metal-catalyzed intermolecular reaction of carbonyl reagents with alkynes is one of the efficient methods for synthesizing carbonyl-containing valuable products. This review summarizes the syntheses of -conjugated cyclic carbonyl compounds by the reaction of alkynes with suitable carbonyl reagents in the presence of transition metal catalysts, to afford isocoumarins, chromones, 2-quinolones, 4-quinolones, and isoquinolones.

7.

「配位子周辺部の修飾による新しい遷移金属錯体触媒の開発と触媒反応への応用」
藤原哲晶
有機合成化学協会誌, 2012, 70, 928-936. DOI:10.5059/yukigoseikyokaishi.70.928

Kyoto Univ.

Transition-metal-catalyzed addition reactions of carbonyl compounds to carbon-carbon multiple bonds such as alkynes are environmentally friendly because all atoms of the substrates are retained in the products. In this review, we overview recent results on the transition-metal-catalyzed addition reactions of carbonyl functionalities to alkynes (in Japanese).

6.

"Carbon Dioxide as a Carbon Source in Organic Transformation: Carbon-Carbon Bond Forming Reactions by Transition-Metal Catalysts" (Feature Article)
Yasushi Tsuji,* Tetsuaki Fujihara
Chem. Commun., 2012, 48, 9956-9964. DOI:10.1039/C2CC33848C

Kyoto Univ.

Recent carbon-carbon bond forming reactions of carbon dioxide with alkenes, alkynes, dienes, aryl zinc compounds, aryl boronic esters, aryl halides, arenes having acidic C-H bonds are reviewed in which transition-metal catalysts play an important role.

5.

「遷移金属錯体によるカルボニル官能基のアルキンへの付加反応」
辻 康之,藤原哲晶
有機合成化学協会誌, 2011, 69, 1375-1388. DOI:10.5059/yukigoseikyokaishi.69.1375

Kyoto Univ.

We set out to expand catalytic environment to nanosize by modification of ligands. The recent progress in homogeneous transition-metal catalysts with nanosize ligands is overviewed. To expand a molecular size, dendritic frameworks including flexible or rigid moieties, sterically congested m-terphenyl and its higher dendritic framework were introduced onto N-heterocyclic carbene and phosphine ligands (in Japanese).

4.

"Transition-Metal-Catalyzed Additions of Carbonyl Functionalities to Alkynes" (Account)
Tetsuaki Fujihara, Tomohiro Iwai, Jun Terao, Yasushi Tsuji*
Synlett, 2010, 2537-2548. DOI:10.1055/s-0030-1258776

Kyoto Univ.

Transition-metal-catalyzed transformations between carbonyl compounds and carbon-carbon unsaturated bonds are important and attractive. In this Account, we describe our recent results on the iridium- and palladium-catalyzed additions of acid chlorides, carbamoyl chlorides, and formamides to alkynes.

3.

"Recent Development of Homogeneous Transition Metal Catalysts with Nanosize Ligands" (Highlight Review)
Yasushi Tsuji,* Tetsuaki Fujihara
Chem. Lett., 2007, 36, 1296-1301. DOI:10.1246/cl.2007.1296

Kyoto Univ.

Expanding catalytic environment to a nanosize is one of the most promising ways to improve performance of homogeneous catalysts. In this highlight review, recent development in homogeneous transition metal catalysts with well-defined nanosize ligands is overviewed. These systems realize efficient catalysts with remarkable enhancement of catalytic activity, suppression of metal aggregation, and unprecedented selectivity.

2.

"Homogeneous Nanosized Palladium Catalysts"(Forum Article)
Yasushi Tsuji,* Tetsuaki Fujihara
Inorg. Chem., 2007, 46, 1895-1902. DOI:10.1021/ic061872q

Kyoto Univ.

Expanding catalytic environment to a nanosize must be one of the most promising ways to improve performance of homogeneous catalysts. In this forum article, recent development in homogeneous nanosize palladium catalysts is overviewed. It contains solubilized palladium nanoparticles, metalated dendrimers, and complexes with well-defined nanosized ligands. These systems realize efficient catalyst recycling, unique selectivity, suppression of metal aggregation, and remarkable enhancement of catalytic activity.

1.

"New Design in Homogeneous Palladium Catalysis: Study of Transformation of Group 14 Element Compounds and Development of Nanosize Palladium Catalysts"(Special Issue for Prof. Sang Chul Shim)
Yasushi Tsuji,* Tetsuaki Fujihara
Bull. Korean Chem. Soc., 2007, 27, 1902-1909. DOI:10.5012/bkcs.2007.28.11.1902

Kyoto Univ.

We describe the new design in reactions of Group 14 element compounds and in homogeneous nanosize Pd catalysts. In the early stages of our study, we developed Pd-catalyzed transformations of allylic esters with disilanes, silylcyanides and acylsilanes to the corresponding silylation, cyanation and acylation products, respectively. We also developed a Pd-catalyzed three component coupling reaction of Group 14 element compounds involving 1,3-diene and acid chlorides to form , -unsaturated ketone as a single product. Recently, we focus our attention on modifying the catalytic environment by nanosize Pd in order to improve the performance of Pd catalysts. These nanosystems realize efficient catalytic environment with remarkable enhancement in catalytic activity and unprecedented selectivity.

解説・その他

Last Update 27.10.2010

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