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TATSUYA UCHIDA Last modified date:2018.06.14

Associate Professor / Division for Arts and Science
Division for Experimental Natural Science
Faculty of Arts and Science


Graduate School
Undergraduate School
Other Organization


Homepage
http://www.science.scc.kyushu-u.ac.jp/index.html
Phone
092-802-6022
Fax
092-802-6022
Academic Degree
Dr. of Sci.
Country of degree conferring institution (Overseas)
No
Field of Specialization
organic synthesis
Total Priod of education and research career in the foreign country
00years00months
Research
Research Interests
  • the development of environment friendly asymmetric reaction using transition metal complexes as catalysts
    keyword : Catalytic asymmetric reaction
    2013.10~2013.10.
Academic Activities
Reports
1. RYO IRIE, TATSUYA UCHIDA, KAZUHIRO MATSUMOTO, Katsuki Catalysts for Asymmetric Oxidation: Design Concepts, Serendipities for Breakthroughs, and Applications, Chemical Letters, 2015.08.
2. TATSUYA UCHIDA, Tsutomu Katsuki, Asymmetric nitrene transfer reactions: sulfimidation, aziridination and C-h amination using azide compounds as nitrene precursors, The Chemical Record, 2014.02, Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give nitrene species by releasing nitrogen, are ideal precursors but rather stable. Their decomposition needs UV irradiation, heating in the presence of a metal complex, or Lewis acid treatment. The examples of previous azide decomposition prompted us to examine Lewis acid and low-valent transition-metal complexes as catalysts for azide decomposition. Thus, we designed new ruthenium complexes that are composed of a low-valent Ru(II) ion, apical CO ligand, and an asymmetry-inducing salen ligand. With these ruthenium complexes and azides, we have achieved highly enantioselective nitrene transfer reactions under mild conditions. Recently, iridium-salen complexes were added to our toolbox..
3. TATSUYA UCHIDA, Tsutomu Katsuki, Green Asymmetric Oxidation Using Air as Oxidant, Synthetic Organic Chemistry Japan, 2013.11, Nitrogen functional groups are found in many biologically active compounds and their stereochemistry has a profound effect on biological activity. Nitrene transfer reactions such as aziridination, C-H bond amination, and sulfimidation are useful methods for introducing nitrogen functional groups, and the enantiocontrol of the reactions has been extensively investigated. Although high enantioselectivity has been achieved, most of the reactions use (N-arylsulfonylimino)phenyliodinane, which co-produces iodobenzene, as a nitrene precursor and have a low atom economy. Azide compounds, which give We found that (NO)- and (aqua)ruthenium-salen complexes are efficient catalysts for the asymmetric aerobic oxygen atom transfer reactions such as epoxidation and sulfoxidation at ambient temperature. (NO)ruthenium-salen complexes 2 and 3 could catalyze oxidation of sulfides and the epoxidation of conjugated olefins with good to high enantioselectivity using dioxygen as oxidant, albeit under visible light-irradiation, respectively. On the other hand, (aqua)ruthenium-salen complex 5 was found to catalyze highly enantioselective epoxidation in air even without irradiation. Although the mechanism of this ruthenium-catalyzed aerobic oxidation has not been completely elucidated, water that is bound to the ruthenium ion has been considered to play a critical role in proton coupled electron transfer, a key step for oxygen activation, and to be regenerated via oxo-hydroxo tautomerization. We also found that (di-μ-hydroxo)iron-salan complexes catalyzes asymmetric dehydrogenative oxidation reactions such as 2-naphthol coupling, alcohol oxidation, and dearomatization, using air as oxidant..
Papers
1. KIM CHUNG SIK, Takuya Oguma, Chisaki Fujitomo, TATSUYA UCHIDA, Tsutomu Katsuki, Iron-Catalyzed Asymmetric Aerobic Oxidative Dearomatizing Spirocyclization of Methylenebis(arenol)s, The Chemical Society of Japan, 10.1246/cl.160680, 45, 1262-1264, 2016.08, Iron(salan) complexes are efficient catalysis in intramolecular aerobic oxidative dearomatizing spirocyclization of methylenebis(arenol)s, which was prepared from salicyl akdehydes and phenols with simple microwave irradiation. Under the iron-catalyzed aerobic oxidation conditions, methylenebis(arenol)s converted to the corresponding spirocyclic compounds with good to high enantioselectivity (up to 87% ee)..
2. Hirotaka Mizoguchi, TATSUYA UCHIDA, Tsutomu Katsuki, Ruthenium-Catalyzed Oxidative Kinetic Resolution of Unactivated and Activated Secondary Alcohols with Air as the Hydrogen Acceptor at Room Temperature., ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201310426, 53, 3178-3182, 2014.02, Enantiopure alcohols are versatile building blocks for asymmetric synthesis and the kinetic resolution (KR) of racemic alcohols is a reliable method for preparing them. Although many KR methods have been developed, oxidative kinetic resolution (OKR), in which dioxygen is used as the hydrogen acceptor, is the most atom-efficient. Dioxygen is ubiquitous in air, which is abundant and safe to handle. Therefore, OKR with air has been intensively investigated and the OKR of benzylic alcohols was recently achieved by using an Ir catalyst without any adjuvant. However, the OKR of unactivated alcohols remains a challenge. An [(aqua)Ru- (salen)] catalyzed OKR with air as the hydrogen acceptor was developed, in which the aqua ligand is exchanged with alcohol and the Ru complex undergoes single electron transfer to dioxygen and subsequent alcohol oxidation. This OKR can be applied without any adjuvant to activated and unactivated alcohols with good to high enantioselectivity. The unique influence of substrate inhibition on the enantioselectivity of the OKR is also described..
3. Yota Nishioka, TATSUYA UCHIDA, Tsutomu Katsuki, Enantio- and Regioselective Intermolecular Benzylic and Allylic C-H Bond Amination, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 10.1002/anie.201208906, 52, 6, 1739-1742, 2013.01, We designed new ruthenium catalysts that were composed of ruthenium(II) ion, apical CO ligand, and highly enantioselective salen ligand and could for the first time achieve highly enantioselective sulfimidation, aziridination, and C-H amination using azide compounds as the nitrene precursors. Catalytic activity, stereoselectivity, and regioselectivity of the ruthenium catalysts were remarkably improved by an appropriate tuning of salen ligand..
4. Yasuaki Fukunaga, TATSUYA UCHIDA, Yutaro Ito, Tsutomu Katsuki, Ru(CO)-salen-Catalyzed Synthesis of Enantiopure Aziridinyl Ketones and Formal Asymmetric Synthesis of (+)-PD 128907, ORGANIC LETTERS, 10.1021/ol302095r, 14, 17, 4658-4661, 2012.09, Aziridination of vinyl ketones using SESN3 in the presence Ru(CO)-salen complex 1 provides the enantiopure aziridinyl ketones that can serve as useful chiral building blocks. A formal asymmetric synthesis of (þ)-PD 128907 was achieved in an eight-step sequence via aziridination..
5. Shota Koya, Yota Nishioka, Hirotaka Mizoguchi, Tatsuya Uchida, Tsutomu Katsuki, Asymmetric Epoxidation of Conjugated Olefins with Dioxygen, Angew. Chem. Int. Ed., 10.1002/anie.201201848, 51, 33, 8243-8246, 2012.07, A complex situation: Asymmetric epoxidation of conjugated olefins was achieved at room temperature using ruthenium complex 1 as the catalyst and air as the oxidant to give epoxides in up to 95 % ee. When the product was acid sensitive, the reaction was carried out at 0 °C under oxygen..
6. Chungsik Kim, Tatsuya Uchida, Tsutomu Katsuki, Asymmetric olefin aziridination using a newly designed Ru(CO)(salen) complex as the catalyst, Chem. Commun, 10.1039/c2cc32997b, 48, 7188–7190, 2012.04, Highly enantioselective and good to high-yielding aziridination of conjugated and non-conjugated terminal olefins and cyclic olefins was achieved using a newly designed Ru(CO)(salen) complex as the catalyst in the presence of SESN3 under mild conditions..
7. Masami Ichinose, Hidehiro Suematsu, Yoichi Yasutomi, Yota Nishioka, Tatsuya Uchida, and Tsutomu Katsuki, Enantioselective Intramolecular Benzylic CーH Bond Amination:
Efficient Synthesis of Optically Active Benzosultams, Angew. Chem. Int. Ed, 10.1002/anie.201101801, 50, 9884-9887, 2011.09.
8. Tanaka, H., Nishikawa, H., Uchida, T. & Katsuki, T., , Photopromoted Ru-Catalyzed Asymmetric Aerobic Sulfide Oxidation and Epoxidation Using Water as a Proton Transfer Mediator., J. Am. Chem. Soc, 10.1021/ja104184r, 132, 34, 12034-12041, 2010.05, 著者等は、光学活性なルテニウム(ニトロシル)サレン錯体が、室温、常圧の温和な条件下で還元剤を用いること無しに、分子状酸素を酸化剤とするオレフィンの不斉エポキシ化、スルフィドの不斉スルホキシ化に成功した。可視光照射条件下において、錯体2を触媒とすることで不斉スルホキシ化が最高98% eeのエナンチオ選択性にて、また錯体3を用いることにて不斉エポキシ化が76-92% eeの不斉収率にて目的とする酸化生成物が得られた。
本反応では、反応系中に存在する水分子が、ルテニウムイオンに配位し、プロトン供給源として分子状酸素活性化の一翼を担い、また、消費された水は反応サイクル中で再生するものと考えられる。.
9. Tatsuya Uchida, Tstomu Katsuki, Construction of a new type of chiral bidentate NHC ligands: copper-catalyzed asymmetric conjugate alkylation, Tetrahedron Letters, 2009.06.
10. Mizoguchi Takahiro, Ishida Koichi, Uchida Tatsuya, Katsuki Tsutomu , Ru-salen complex catalyzed chemoselective aerobic oxidation of primary alcohols to aldehydes, Tetrahedron Letters, 2009.06.
11. H. Suematsu, S. Kanchiku, T. Uchida, T. Katsuki, Construction of Aryliridium-salen Complexes: Enantio- and Cis-Selective Cyclopropanation of Conjugated and Nonconjugated Olefins, J. Am. Chem. Soc, 130, 10327-10337, 2008.12.
12. S. Kanchiku, H. Suematsu, K. Matsumoto, T. Uchida, T. Katsuki, Construction of an Aryliridium-Salen Complex for Highly cis- and Enantioselective Cyclopropanations, Angew. Chem. Int. Ed, early view , 2007.04.
13. H. Kawabata, K. Omura, T. Uchida, T. Katsuki, Construction of robust ruthenium(salen)(CO) complexes and asymmetric aziridination with nitrene precursors in the form of azide compounds that bear easily removable N-sulfonyl groups. , Chemistry -An Asian Journal, 2(2), 248-256, 2007.04.
14. Omura Kazuhumi, Murakami Masakazu, Uchida Tatsuya, Katsuki Tsutomu, Enantioselective aziridination and amination using p-toluenesulfonyl azide in the presence of Ru(salen)(CO) complex, CHEMISTRY LETTERS, 32, 4, 354-355, 32巻4号、p. 354-355, 2003.04.
Presentations
1. 内田 竜也, Site-selective Asymmetric C−H Bond Functionalization, The 1st Sino-Japanese Symposium on Catalysis for Precision Synthesis, 2018.05.
2. 内田 竜也, Activation of Molecular Oxygen and Catalytic Asymmetric Aerobic Oxidation, 第1回精密制御反応場国際シンポジウム, 2016.07, Molecular oxygen (O2) is an ubiquitous, abundant, and highly atom economic oxidant on the earth. However, most of O2 activation required heating and/or pressurizing conditions or the addition of co-reductant, unfortunately. Stereoselectivities of these oxidations are insufficient. On the other hand, typical biological oxidation proceeded with complete stereoselectivity albeit with consuming 2H+ and 2e- and producing water as a waste material. Thus, development of new methodology for O2 activation has been strongly required. Herein, we presented ruthenium-catalyzed highly enantioselective aerobic oxidation such as epoxidation and oxidative kinetic resolution of alcohol.
Under aqueous conditions, ruthenium-salen complexes can activate O2 to active oxygen spices such as corresponding superoxide and oxo spices via single-electron-transfer (SET) and proton-coupled- electron-transfer (PCET) with water mediation, and catalyze epoxidation of trans- -methylstyrene derivatives with good to high enantioselectivity (up to 95% ee).1b On the other hand, under alcoholic conditions, racemic sec-alcohol was oxidized with high enantiomer differentiation (krel = up to 60).1a It was noteworthy that ruthenium-salen complexes catalyzed aerobic oxidations are proceed under ambient conditions without any activation methods..
3. 内田 竜也, Development of Catalytic C-C Bond Formation, I2CNER International Workshop -Natural and Chemical Catalysts for Technology-, 2017.02, C-H bond functionalization via carbene transfer reaction is one of strong and useful tool for the construction of carbon framework and has garner much attention. However, C-H bond, which is ubiquitous and abundant in organic molecule, is still difficult to convert desired function group at well. Herein, we found that (aryl)iridium(salen) complexes are efficient catalysis in C-H functionalization.1 (Aryl)iridium complex can decompose -aryl- -dizaoacetates to desired carbene intermediates and convert benzylic, allylic, and propargylic C-H bond to the corresponding C-C bond with excellent diastereo- and enantio-selectivities. Furthermore, iridium-catalyzed C-H insertion reactions showed interesting site-selectivity. That reaction carried out at only methylene C-H bond on ethyl group..
4. , [URL].
5. Asymmetric Baeyer-Villiger Oxidation Using Metallosalen Complex as Catalyst.
6. Asymmetric Aziridination Using Azide Compounds as Nitrene Precursor in the Presence of Robust Ru(salen) Complex.