Dehydrogenative Oxidation of Alcohols Promoted by Multi-functionalized Iron Complex

• Project/Area Number: 16K17880
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Kitasato University
• Principal Investigator: KAMITANI Masahiro 北里大学, 理学部, 助教 (40758447)
• Project Period (FY): 2016-04-01 – 2019-03-31
• Project Status: Completed (Fiscal Year 2018)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2018: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2017: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
• Keywords: 鉄錯体 / 水素発生 / アルコール酸化 / 触媒反応 / 有機合成反応 / 水素貯蔵

Outline of Final Research Achievements

Multi-functionalized iron complexes were synthesized in the reaction of iron complex bearing a cyclopentadienyl ligand with pyridinylketone. These complexes exhibited the catalytic activity for the dehydrogenation of various primary and secondary alcohols. Control experiment in the presence of various pyridine derivatives investigated that the introduction of electron-donating group on ligands accelerated the catalytic reaction. Mechanistic study revealed that the key intermediate in the dehydrogenation process and the role of functional group on the ligands.

Academic Significance and Societal Importance of the Research Achievements

本研究の目的であるアルコールの水素発生型酸化反応は廃棄物の少ないケトン、アルデヒド化合物合成法として有用であることに加え、アルコールの水素貯蔵媒体としても利用可能な化学変換プロセスである。本反応を効率的に進行させる手法が開発できれば、クリーンな化学プロセスの開発や、新エネルギー媒体として注目を集めている水素エネルギー利用に向けた基礎的知見が得られる。よって、学術、産業両分野への広い波及効果が期待できる。

Research Products

• [Journal Article] Facile Entry to Iron Complexes Supported by Quinoline-Based PNN Pincer Ligand (2018)
  • Author(s): Kamitani Masahiro、Kusaka Haruki、Toriyabe Takumi、Yuge Hidetaka
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 91 Issue: 9 Pages: 1429-1435
  • DOI: 10.1246/bcsj.20180124
  • NAID: 130007484402
  • Peer Reviewed
• [Journal Article] Dihydride Iron Complex Bearing a Silyl-Tethered Cyclopentadienyl Ligand (2018)
  • Author(s): Masahiro Kamitani, Yoshinori Nishiguchi, Masumi Itazaki, Hiroshi Nakazawa
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 91 Issue: 4 Pages: 588-593
  • DOI: 10.1246/bcsj.20170403
  • NAID: 130006707636
  • Peer Reviewed
• [Journal Article] Direct C-H Functionalization of Methane by Homogeneous Catalysis (2017)
  • Author(s): Kamitani Masahiro
  • Journal Title: Journal of Synthetic Organic Chemistry, Japan Volume: 75 Issue: 12 Pages: 1290-1291
  • DOI: 10.5059/yukigoseikyokaishi.75.1290
  • NAID: 130006248365
  • ISSN: 0037-9980, 1883-6526
  • Peer Reviewed
• [Journal Article] Polyhydrides of Sc, Zr and Hf and Their Proposed Formation. (2017)
  • Author(s): Kurogi Takashi、Kamitani Masahiro、Carroll Patrick J.、Mindiola Daniel J.
  • Journal Title: Israel Journal of Chemistry Volume: 57 Issue: 10-11 Pages: 999-1009
  • DOI: 10.1002/ijch.201700062
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Room-Temperature Ring-Opening of Quinoline, Isoquinoline, and Pyridine with Low-Valent Titanium (2017)
  • Author(s): Baek Seung-yeol、Kurogi Takashi、Kang Dahye、Kamitani Masahiro、Kwon Seongyeon、Solowey Douglas P.、Chen Chun-Hsing、Pink Maren、Carroll Patrick J.、Mindiola Daniel J.、Baik Mu-Hyun
  • Journal Title: Journal of the American Chemical Society Volume: 139 Issue: 36 Pages: 12804-12814
  • DOI: 10.1021/jacs.7b07433
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Reactivity Studies of a Zirconium Methylidene Complex. Group Transfer and Methylenation Reactions (2017)
  • Author(s): Kurogi Takashi, Masahiro Kamitani, Brian C. Manor, Patrick J. Carroll, Daniel J. Mindiola
  • Journal Title: Organometallics Volume: 36 Issue: 1 Pages: 74-79
  • DOI: 10.1021/acs.organomet.6b00594
  • Peer Reviewed / Int'l Joint Research
• [Presentation] C-H borylation of Arenes Catalyzed by PNN Iron Pincer Complex (2019)
  • Author(s): Haruki Kusaka, Masahiro Kamitani, Hidetaka Yuge
  • Organizer: The 99th CSJ Annual Meeting
• [Presentation] Transfer Hydrogenation of Alkenes and Alkynes Promoted by Iron Complex Bearing Silyl-Tethered Cyclopentadienyl Ligand (2018)
  • Author(s): Masahiro Kamitani, Masumi Itazaki, Yoshinori Nishiguchi, Hiroshi Nakazawa
  • Organizer: 28th International Conference on Organometallic Chemistry
  • Int'l Joint Research
• [Presentation] Dehydrogenative Oxidation of Alcohols Catalyzed by an Iron Complex (2018)
  • Author(s): Masahiro Kamitani
  • Organizer: 2nd International Conference & Expo on Green Chemistry and Engineering
  • Int'l Joint Research / Invited
• [Presentation] ピリジルキノリノ骨格を持つ PNN ピンサー鉄錯体の合成と反応性 (2018)
  • Author(s): 日下 晴貴、神谷 昌宏、弓削 秀隆
  • Organizer: 錯体化学第68回討論会
• [Presentation] Synthesis and Reactivity of Dihydride Iron Complex Bearing Silyl-Tethered Cyclopentadienyl Ligand (2018)
  • Author(s): Masahiro Kamitani, Yoshinori Nishiguchi, Masumi Itazaki, Hiroshi Nakazawa
  • Organizer: 43rd International Conference on Coordination Chemistry
  • Int'l Joint Research
• [Presentation] SiNN ピンサ－型配位子を有する 10 族遷移金属錯体の反応性 (2018)
  • Author(s): 鳥谷部 拓海、斎藤 誉人、神谷 昌宏、弓削 秀隆
  • Organizer: 第22回ケイ素化学協会シンポジウム
• [Presentation] SiNN 型ピンサー配位子を有するニッケル錯体を用いたハロゲン化アリールのボリル化反応 (2018)
  • Author(s): 鳥谷部 拓海、神谷 昌宏、弓削 秀隆
  • Organizer: 日本化学会第98春季年会
• [Presentation] 鉄触媒によるアルコールの脱水素的酸化 (2018)
  • Author(s): 神谷 昌宏
  • Organizer: 大阪市立大学理学部セミナー
  • Invited
• [Presentation] Transfer Hydrogenation of Alkenes and Alkynes Promoted by Iron Complex Bearing Silyl-Tethered Cyclopentadienyl Ligand (2018)
  • Author(s): Masahiro Kamitani, Masumi Itazaki, Yoshinori Nishiguchi, Hiroshi Nakazawa
  • Organizer: XXVIII International Conference on Organometallic Chemistry (ICOMC2018)
  • Int'l Joint Research
• [Presentation] Dehydrogenative Oxidation of Alcohols Catalyzed by an Iron Complex (2018)
  • Author(s): Masahiro Kamitani
  • Organizer: 2nd International Conference & Expo on Green Chemistry and Engineering (ICEGCE2018)
  • Int'l Joint Research / Invited
• [Presentation] Synthesis and Reactivity of Dihydride Iron Complex Bearing Silyl-Tethered Cyclopentadienyl Ligand (2018)
  • Author(s): Masahiro Kamitani, Yoshinori Nishiguchi, Masumi Itazaki, Hiroshi Nakazawa
  • Organizer: International Conference on Coordination Chemistry (ICCC) 2018
  • Int'l Joint Research
• [Presentation] Acceptorless Alcohol Dehydrogenation Catalysed by an Iron Complex Bearing 2-Pyridinyl Benzylalcohol (2017)
  • Author(s): Masahiro Kamitani, Soichiro Suzuki, Masumi Itazaki, Hiroshi Nakazawa, Hidetaka Yuge
  • Organizer: 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Place of Presentation: Melbourne Convention and Exhibition Centre (Australia Melbourne)
  • Year and Date: 2017-07-23
  • Int'l Joint Research
• [Presentation] 2-ピリジニルベンジルアルコールを non-innocent 配位子として有する鉄錯体による触媒的アルコール脱水素反応 (2017)
  • Author(s): 鈴木 聡一郎、神谷 昌宏、中沢 浩、弓削 秀隆
  • Organizer: 第97日本化学会春季年会
  • Place of Presentation: 慶應義塾大学日吉キャンパス（神奈川県横浜市）
  • Year and Date: 2017-03-16
• [Presentation] 2-ベンゾイルピリジン誘導体をnon-innocent配位子とする鉄錯体による触媒的アルコール脱水素反応 (2017)
  • Author(s): 鈴木 総一郎、神谷 昌宏、中沢 浩、弓削 秀隆
  • Organizer: 第10回北里化学シンポジウム
• [Presentation] SiNN 型ピンサー配位子を有するニッケルボリル錯体の合成と反応性 (2017)
  • Author(s): 鳥谷部 拓海、神谷 昌宏、弓削 秀隆
  • Organizer: 第10回北里化学シンポジウム
• [Presentation] SiNN ピンサ－型配位子を有するニッケル錯体の合成と反応性 (2017)
  • Author(s): 鳥谷部 拓海、神谷 昌宏、弓削 秀隆
  • Organizer: 錯体化学会第67回討論会
• [Presentation] Iron-Catalyzed Selective Hydrophosphonation of Alkynes and Vinylphosphines (2017)
  • Author(s): Hiroshi Nakazawa, Masumi Itazaki, Masahiro Kamitani
  • Organizer: 6th Latin American Symposium on Coordination and Organometallic Chemistry
  • Int'l Joint Research / Invited
• [Presentation] Acceptorless Alcohol Dehydrogenation Catalysed by an Iron Complex Bearing 2-Pyridinyl Benzylalcohol (2017)
  • Author(s): Masahiro Kamitani, Soichiro Suzuki, Masumi Itazaki, Hiroshi Nakazawa, Hidetaka Yuge
  • Organizer: The 6th Asian Conference on Coordination Chemistry (ACCC6)
  • Int'l Joint Research
• [Presentation] Non-innocent 配位子を有する鉄錯体触媒によるアルコール脱水素反応 (2016)
  • Author(s): 鈴木 聡一郎、神谷 昌宏、小林 真道、中沢 浩、弓削 秀隆
  • Organizer: 錯体化学会第66回討論会
  • Place of Presentation: 福岡大学七隈キャンパス（福岡市城南区）
  • Year and Date: 2016-09-10
• [Presentation] 鉄錯体によるアルコールの触媒的脱水素酸化反応 (2016)
  • Author(s): 神谷 昌宏
  • Organizer: 大阪市立大学理学部セミナー
  • Place of Presentation: 大阪市立大学杉本キャンパス （大阪市住吉区）
  • Invited
• [Remarks] 神谷 昌宏（北里研究者登録情報)
  • URL: http://kerid-web.kitasato-u.ac.jp/Profiles/91/0009081/profile.html
• [Remarks] 分子構築学講座ＨＰ
  • URL: https://www.kitasato-u.ac.jp/sci/resea/kagaku/HP_kochiku/
• [Remarks] 北里大学理学部化学科分子構築学講座研究室ＨＰ
  • URL: https://www.kitasato-u.ac.jp/sci/resea/kagaku/HP_kochiku/
• [Patent(Industrial Property Rights)] ３座配位子を有する鉄錯体化合物及びその製造方法、並びに有機ボロン酸エステルの製造方法 (2019)
  • Inventor(s): 神谷 昌宏
  • Industrial Property Rights Holder: 神谷 昌宏
  • Industrial Property Rights Type: 特許
  • Filing Date: 2019
• [Patent(Industrial Property Rights)] 有機ケイ素化合物の製造方法 (2018)
  • Inventor(s): 中沢 浩、神谷 昌宏、佐藤 一彦、中島 裕美子
  • Industrial Property Rights Holder: 中沢 浩、神谷 昌宏、佐藤 一彦、中島 裕美子
  • Industrial Property Rights Type: 特許
  • Filing Date: 2018