Shun-ichi Murahashi

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Organization: Okayama University of Science

Department: 1 Department of Chemistry, Graduate School of Engineering Science

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References

Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine

Co-reporter:Shun-Ichi Murahashi, Dazhi Zhang, Hiroki Iida, Toshio Miyawaki, Masaaki Uenaka, Kenji Murano and Kanji Meguro

Chemical Communications 2014 vol. 50(Issue 71) pp:10295-10298

Publication Date(Web):18 Jul 2014

DOI:10.1039/C4CC05216A

An efficient and practical catalytic method for the aerobic oxidative transformation of sulfides into sulfoxides, and thiols into disulfides with formic acid/TEA in the presence of a new, readily available, and stable flavin catalyst 5d is described.

Copper-catalyzed aerobic oxidative functionalization of C–H bonds of alkanes in the presence of acetaldehyde under mild conditions

Co-reporter:Yukiko Hayashi, Naruyoshi Komiya, Ken Suzuki, Shun-Ichi Murahashi

Tetrahedron Letters 2013 Volume 54(Issue 21) pp:2706-2709

Publication Date(Web):22 May 2013

DOI:10.1016/j.tetlet.2013.03.074

Copper-catalyzed oxidative functionalization of C–H bonds of alkanes with molecular oxygen has been performed in the presence of Cu(OAc)2 catalyst and acetaldehyde in acetonitrile at 70 °C with extremely high turn-over numbers.

Oxidation of Primary Amines to Oximes with Molecular Oxygen using 1,1-Diphenyl-2-picrylhydrazyl and WO3/Al2O3 as Catalysts

Co-reporter:Ken Suzuki, Tomonari Watanabe, and Shun-Ichi Murahashi

The Journal of Organic Chemistry 2013 Volume 78(Issue 6) pp:2301-2310

Publication Date(Web):February 26, 2013

DOI:10.1021/jo302262a

The oxidative transformation of primary amines to their corresponding oximes proceeds with high efficiency under molecular oxygen diluted with molecular nitrogen (O2/N2 = 7/93 v/v, 5 MPa) in the presence of the catalysts 1,1-diphenyl-2-picrylhydrazyl (DPPH) and tungusten oxide/alumina (WO3/Al2O3). The method is environmentally benign, because the reaction requires only molecular oxygen as the terminal oxidant and gives water as a side product. Various alicyclic amines and aliphatic amines can be converted to their corresponding oximes in excellent yields. It is noteworthy that the oxidative transformation of primary amines proceeds chemoselectively in the presence of other functional groups. The key step of the present oxidation is a fast electron transfer from the primary amine to DPPH followed by proton transfer to give the α-aminoalkyl radical intermediate, which undergoes reaction with molecular oxygen and hydrogen abstraction to give α-aminoalkyl hydroperoxide. Subsequent reaction of the peroxide with WO3/Al2O3 gives oximes. The aerobic oxidation of secondary amines gives the corresponding nitrones. Aerobic oxidative transformation of cyclohexylamines to cyclohexanone oximes is important as a method for industrial production of ε-caprolactam, a raw material for Nylon 6.

Ruthenium-Catalyzed Oxidative Dearomatization of Phenols to 4-(tert-Butylperoxy)cyclohexadienones: Synthesis of 2-Substituted Quinones from p-Substituted Phenols

Co-reporter:Shun-Ichi Murahashi;Noriko Miyaguchi;Shinji Noda;Takeshi Naota;Akiko Fujii;Yasutaka Inubushi;Naruyoshi Komiya

European Journal of Organic Chemistry 2011 Volume 2011( Issue 27) pp:5355-5365

Publication Date(Web):

DOI:10.1002/ejoc.201100740

Abstract

The ruthenium-catalyzed oxidation of phenols with tert-butylhydroperoxide efficiently gives the corresponding 4-(tert-butylperoxy)cyclohexadienones. The oxidation proceeds selectively because of ruthenium's ability for rapid single-electron transfer. This biomimetic oxidation reaction is highly useful to obtain the metabolic compounds desired for confirming the safety of medicines and related compounds. Typically, the first metabolic compound of the female hormone estrone is readily obtained by this biomimetic oxidation reaction. The resulting 4-(tert-butylperoxy)cyclohexadienones are versatile synthetic intermediates, which can be transformed into 2-substituted 1,4-benzoquinones by treatment with acid catalysts. Acid-promoted rearrangement followed by a Diels–Alder reaction provides a new strategy for the synthesis of fused cyclic compounds, such as naphthoquinone and anthraquinone derivatives, from readily available phenols. The nonnatural 1,4-diacetoxy steroidal skeleton is obtained by the oxidation of estrone followed by zinc-mediated migration. Vitamin K₃ is synthesized selectively from p-cresol in an overall 79 % yield in 4 steps, and the synthesis includes the ruthenium-catalyzed oxidation.

Rhenium-Catalyzed Addition of Carbonyl Compounds to the Carbon−Nitrogen Triple Bonds of Nitriles: α-C−H Activation of Carbonyl Compounds

Co-reporter:Hikaru Takaya ; Masatsugu Ito

Journal of the American Chemical Society 2009 Volume 131(Issue 31) pp:10824-10825

Publication Date(Web):July 16, 2009

DOI:10.1021/ja9036669

The ReH7(PPh3)2-catalyzed addition of carbonyl compounds to the carbon−nitrogen bond of nitriles proceeds efficiently and selectively to give the corresponding (Z)-enamines, which are important synthetic intermediates. The key step of the reaction is the chemoselective α-C−H activation of carbonyl compounds induced by the α-heteroatom effect in the presence of nitriles.

Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes: A CH Bond Activation to the Trifluoromethyl Group

Co-reporter:Yong Guo Dr.;Xiaming Zhao Dr.;Dazhi Zhang Dr. Dr.

Angewandte Chemie 2009 Volume 121( Issue 25) pp:

Publication Date(Web):

DOI:10.1002/ange.200990132

No abstract is available for this article.

Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes: A CH Bond Activation to the Trifluoromethyl Group

Co-reporter:Yong Guo Dr.;Xiaming Zhao Dr.;Dazhi Zhang Dr. Dr.

Angewandte Chemie 2009 Volume 121( Issue 11) pp:

Publication Date(Web):

DOI:10.1002/ange.200805852

Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes: A CH Bond Activation to the Trifluoromethyl Group

Co-reporter:Yong Guo Dr.;Xiaming Zhao Dr.;Dazhi Zhang Dr. Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 25) pp:

Publication Date(Web):

DOI:10.1002/anie.200990130

No abstract is available for this article.

Iridium-Catalyzed Reactions of Trifluoromethylated Compounds with Alkenes: A CH Bond Activation to the Trifluoromethyl Group

Co-reporter:Yong Guo Dr.;Xiaming Zhao Dr.;Dazhi Zhang Dr. Dr.

Angewandte Chemie International Edition 2009 Volume 48( Issue 11) pp:

Publication Date(Web):

DOI:10.1002/anie.200805852

Ruthenium catalyzed biomimetic oxidation in organic synthesis inspired by cytochrome P-450

Co-reporter:Shun-Ichi Murahashi and Dazhi Zhang

Chemical Society Reviews 2008 vol. 37(Issue 8) pp:1490-1501

Publication Date(Web):16 Jun 2008

DOI:10.1039/B706709G

Simulation of the function of cytochrome P-450 with low valent ruthenium complex catalysts leads to the discovery of biomimetic, catalytic oxidation of various substrates selectively under mild conditions. The reactions discussed in this tutorial review are simple, clean, and practical. The principle of these reactions is fundamental and gives wide-scope and environmentally benign future practical methods.

Aerobic Oxidation of Primary Amines to Oximes Catalyzed by DPPH and WO3/Al2O3

Co-reporter:Ken Suzuki;Tomonari Watanabe Dr.

Angewandte Chemie International Edition 2008 Volume 47( Issue 11) pp:2079-2081

Publication Date(Web):

DOI:10.1002/anie.200705002

Flavin-Catalyzed Oxidation of Amines and Sulfides with Molecular Oxygen: Biomimetic Green Oxidation

Co-reporter:Yasushi Imada Dr.;Hiroki Iida Dr.;Satoshi Ono;Yoshiyuki Masui Dr. Dr.

Chemistry – An Asian Journal 2006 Volume 1(Issue 1-2) pp:

Publication Date(Web):10 JUL 2006

DOI:10.1002/asia.200600080

Flavin-catalyzed green oxidation of heteroatom compounds such as sulfides and amines with molecular oxygen and even air in the presence of hydrazine monohydrate in a fluorous solvent such as 2,2,2-trifluoroethanol at room temperature gives the corresponding oxidation products highly efficiently and selectively along with water and molecular nitrogen, which are environmentally benign by-products. The proposed reaction mechanism is based on the kinetics, solvent effect, and redox properties of flavin catalysts.

Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Hydrogen Peroxide and Sodium Cyanide

Co-reporter:Shun-Ichi Murahashi, Naruyoshi Komiya,Hiroyuki Terai

Angewandte Chemie International Edition 2005 44(42) pp:6931-6933

Publication Date(Web):

DOI:10.1002/anie.200501496

An Aerobic, Organocatalytic, and Chemoselective Method for Baeyer–Villiger Oxidation

Co-reporter:Yasushi Imada Dr.;Hiroki Iida Dr.;Takeshi Naota Dr.

Angewandte Chemie International Edition 2005 Volume 44(Issue 11) pp:

Publication Date(Web):3 FEB 2005

DOI:10.1002/anie.200462429

Highly chemoselective Baeyer–Villiger oxidations can be performed in the presence of other reactive functionalities such as alcohols, olefins, and sulfides, which would undergo electrophilic oxidation under conventional conditions (see scheme). [DMRFlEt]⁺[ClO₄]⁻ (depicted blue) is a new class of flavin compound that catalyzes aerobic Baeyer–Villiger oxidations in the presence of Zn dust as the electron source.

Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Hydrogen Peroxide and Sodium Cyanide

Co-reporter:Shun-Ichi Murahashi Dr.;Naruyoshi Komiya Dr.;Hiroyuki Terai

Angewandte Chemie 2005 Volume 117(Issue 42) pp:

Publication Date(Web):29 SEP 2005

DOI:10.1002/ange.200501496

Vielseitige Zwischenstufen zur Synthese von N-Aryl-α-aminosäuren und N,N-disubstituierten 1,2-Diaminen sind durch Ruthenium-katalysierte oxidative Cyanierung von tertiären Aminen zugänglich. Die Verwendung von Wasserstoffperoxid als Oxidationsmittel in Gegenwart von NaCN/AcOH oder HCN liefert die entsprechenden α-Aminonitrile (siehe Schema).

An Aerobic, Organocatalytic, and Chemoselective Method for Baeyer–Villiger Oxidation

Co-reporter:Yasushi Imada Dr.;Hiroki Iida Dr.;Takeshi Naota Dr.

Angewandte Chemie 2005 Volume 117(Issue 11) pp:

Publication Date(Web):3 FEB 2005

DOI:10.1002/ange.200462429

Empfindliche Substrate wie Alkohole, Olefine und Sulfide, die unter gewöhnlichen Baeyer-Villiger-Bedingungen elektrophile Oxidationen eingehen würden, bleiben in einer hoch chemoselektiven katalytischen Baeyer-Villiger-Oxidation unversehrt (siehe Schema). Die Flavin-Verbindung [DMRFlEt]⁺[ClO₄]⁻ (blau) katalysiert die aerobe Baeyer-Villiger-Oxidation in Gegenwart von Zinkstaub.

Catalytic Enantioselective Oxidation of Alkanes and Alkenes Using (Salen)Manganese Complexes Bearing a Chiral Binaphthyl Strapping Unit

Co-reporter:Shun-Ichi Murahashi;Satoru Noji;Naruyoshi Komiya

Advanced Synthesis & Catalysis 2004 Volume 346(Issue 2-3) pp:

Publication Date(Web):29 MAR 2004

DOI:10.1002/adsc.200303190

A (salen)manganese(III) complex bearing a chiral binaphthyl strapping unit catalyzes the enantioselective hydroxylation of indane (up to 34% ee) and the epoxidation of alkenes (up to 93% ee) with iodosylbenzene.

Transition-Metal-Based Lewis Acid and Base Ambiphilic Catalysts of Iridium Hydride Complexes: Multicomponent Synthesis of Glutarimides

Co-reporter:Hikaru Takaya Dr.;Kazunori Yoshida;Katsuhiro Isozaki;Hiroki Terai Dr.

Angewandte Chemie 2003 Volume 115(Issue 28) pp:

Publication Date(Web):16 JUL 2003

DOI:10.1002/ange.200351689

Balanceakt: Der Iridiumkomplex 1 ermöglicht die Durchführung säure- und basenkatalysierter Umsetzungen in einer Eintopfreaktion. Mit ihm können pharmakologisch wichtige Glutarimide in einer Dreikomponenten-Reaktion aus Nitrilen, Alkenen und Wasser aufgebaut werden (siehe Schema).

Transition-Metal-Based Lewis Acid and Base Ambiphilic Catalysts of Iridium Hydride Complexes: Multicomponent Synthesis of Glutarimides

Co-reporter:Hikaru Takaya Dr.;Kazunori Yoshida;Katsuhiro Isozaki;Hiroki Terai Dr.

Angewandte Chemie International Edition 2003 Volume 42(Issue 28) pp:

Publication Date(Web):16 JUL 2003

DOI:10.1002/anie.200351689

Mutual destruction of reagents in acid- and base-promoted reactions in the same container is now avoidable with the iridium polyhydride complex [IrH₅(PiPr₃)₂] (1), which is an ambiphilic Lewis acid and base catalyst. By using catalyst 1, a three-component reaction of nitriles, olefins, and water proceeds efficiently to give glutarimides, which are pharmacologically important (see scheme).

Asymmetric Baeyer–Villiger Reaction with Hydrogen Peroxide Catalyzed by a Novel Planar-Chiral Bisflavin

Co-reporter:Shun-Ichi Murahashi Dr.;Satoshi Ono;Yasushi Imada Dr.

Angewandte Chemie International Edition 2002 Volume 41(Issue 13) pp:

Publication Date(Web):1 JUL 2002

DOI:10.1002/1521-3773(20020703)41:13<2366::AID-ANIE2366>3.0.CO;2-S

The chiral organocatalyst bisflavin 1 catalyzes the asymmetric Baeyer–Villiger reaction of cyclobutanones with H₂O₂ (see scheme). The corresponding lactones are obtained with up to 74 % ee.

Asymmetric Baeyer–Villiger Reaction with Hydrogen Peroxide Catalyzed by a Novel Planar-Chiral Bisflavin

Co-reporter:Shun-Ichi Murahashi Dr.;Satoshi Ono;Yasushi Imada Dr.

Angewandte Chemie 2002 Volume 114(Issue 13) pp:

Publication Date(Web):1 JUL 2002

DOI:10.1002/1521-3757(20020703)114:13<2472::AID-ANGE2472>3.0.CO;2-B

Der chirale Organokatalysator Bisflavin 1 katalysiert asymmetrische Baeyer-Villiger-Reaktionen von Cyclobutanonen mit H₂O₂ (siehe Schema). Die entsprechenden Lactone werden mit bis zu 74 % ee erhalten.

Ruthenium catalyzed biomimetic oxidation in organic synthesis inspired by cytochrome P-450

Co-reporter:Shun-Ichi Murahashi and Dazhi Zhang

Chemical Society Reviews 2008 - vol. 37(Issue 8) pp:NaN1501-1501

Publication Date(Web):2008/06/16

DOI:10.1039/B706709G

Flavin-catalyzed aerobic oxidation of sulfides and thiols with formic acid/triethylamine

Co-reporter:Shun-Ichi Murahashi, Dazhi Zhang, Hiroki Iida, Toshio Miyawaki, Masaaki Uenaka, Kenji Murano and Kanji Meguro

Chemical Communications 2014 - vol. 50(Issue 71) pp:NaN10298-10298

Publication Date(Web):2014/07/18

DOI:10.1039/C4CC05216A