学科名 化学科 講座名 物質化学講座
教員名 今本恒雄
電子メール imamoto@faculty.chiba-u.jp
ホームページ http://org.chem.chiba-u.jp/
（1）
研 究 論 文
原 論 文（2004年以降）
1. Highly Enantioselective Hydrosilylation of Simple Ketones Catalyzed by Rhodium Complexes of P-Chiral Diphosphine Ligands Bearing tert-Butylmethylphosphino Group, T. Imamoto, T. Ito, Y. Yamanoi, R. Narui, K. Yoshida, Tetrahedron: Asymmetry, in press.
2. P-Chiral Tetraphosphine Dirhodium Complex as a Catalyst for Asymmetric Hydrogenation: Synthesis, Structure, Enantioselectivity, and Mechanism. Stereoselective Formation of a Dirhodium Tetrahydride Complex and Its Reaction with Methyl (Z)-a-Acetamidocinnamate, T. Imamoto, K. Yashio, K. V. L. Crépy, H. Takahashi, M. Kouichi, I. D. Gridnev, Organometallics, 25, 908-914 (2006).
3. P-Chiral o-Phosphinophenol as a P/O Hybrid
Ligand: Preparation and Use in Cu-Catalyzed Asymmetric Conjugate Addition of
Diethylzinc to Acyclic Enones, Y. Takahashi, Y. Yamamoto, K. Katagiri, H.
Danjo, K. Yamaguchi, T. Imamoto, J. Org.
Chem., 70, 9009-9012 (2005).
4. An Air-stable
P-Chiral Phosphine Ligand for Highly Enantioselective
Transition-Metal-Catalyzed Reactions, T. Imamoto, K. Sugita, K. Yoshida, J. Am. Chem. Soc., 127, 11934-11935 (2005).
5. A New Synthetic Approach to Phenol Derivatives: Use of
Ring-Closing Olefin Metathesis, K. Yoshida, T. Imamoto, J. Am. Chem. Soc., 127,
10470-10471 (2005).
6. Evidence for
the importance of conformational equilibria in Rh-diphosphine complexes for the
enantioselection in Rh-catalyzed asymmetric hydrogenation, H. Tsuruta, T. Imamoto, K. Yamaguchi, I. D. Gridnev,
Tetrahedron
Lett., 46, 2879-2882 (2005)
7. Nucleophilic Aromatic Substitution Reactions
of Fluorobenzenechromium Complexes with P-Chiral Secondary Phosphine–Boranes:
Synthesis of Optically Pure P-Chiral (Dialkyl)arylphosphine–Boranes, K.
Katagiri, H. Danjo, K. Yamaguchi, T. Imamoto, Tetrahedron, 61,
4701-4704 (2005).
8. Asymmetric Hydrogenation of Enolphosphonates:
Scope and Reaction Mechanism, I. D. Gridnev, M. Yasutake, T. Imamoto, I. P.
Beletskaya, Proc. Natl. Acad. Sci., USA,
101, 5385-5390 (2004).
9. P-Stereogenic P/N
Hybrid Ligands: A Remarkable Switch in Enantioselectivity in
Palladium-Catalyzed Asymmetric Allylation, H. Danjo, M. Higuchi, M. Yada, T.
Imamoto, Tetrahedron Lett., 45, 603-606 (2004)..
10. Optically Active 1,1’-Di-tert-butyl-2,2’-dibenzophosphetanyl: A Highly Strained P-Stereogenic Diphosphine Ligand, T. Imamoto, K. V. L. Crépy, K. Katagiri, Tetrahedron: Asymmetry, (Special Issue), 15, 2213-2218 (2004).
11. Optically Active 1,1-Di-tert-butyl-2,2’-diphosphetanyl and Its Application in Rhodium-Catalyzed Asymmetric Hydrogenations, T. Imamoto, N. Oohara, H. Takahashi, Synthesis (Special Issue), 2004, 1353-1358.
12. Optically Pure 1,2-Bis[(o-alkylphenyl)phosphino]ethanes and Their Use in Rhodium-Catalyzed Asymmetric hydrogenations of a-(acylamino)acrylic Derivatives, T. Imamoto, H. Tsuruta, K. Yamaguchi, I. D. Gridnev, T. Imamoto, Adv. Synth. Catal., 346, 777-788 (2004).
13. Dihydroboronium Derivatives of (S,S)-1,2-Bis(t-butylmethylphosphino)ethane as Convenient Chiral Ligand Precursors, Takahiro Miyazaki, Masanobu Sugawara, Hiroshi Danjo, and Tsuneo Imamoto, Tetrahedron Lett., 45, 9341–9344 (2004).
総 説
1. On the Mechanism of Stereoselection in Rh-Catalyzed asymmetric Hydrogenation: A General Approach for Predicting the Sense of Enantioselectivity, Ilya D. Gridnev, Tsuneo Imamoto, Acc. Chem. Res., 37, 633–644 (2004).
解 説
1. (R,R)-2,3-Bis(tert-butylmethylphosphino)quinoxaline (QiunoxP*)
as a Ligand for Rhodium-Catalyzed Asymmetric Hydrogenation of Prochiral Amino
Acid and Amine Derivatives, T. Imamoto, A. Koide, “Catalysts for the Fine Chemical Industry” Ed. S. Roberts, Wiley, in
press.
2. Preparation of
(S,S)-bis(tert-butylmethylphosphino)ethane ((S,S)-t-Bu-BisP*) as a Rhodium
Complex, K. V. L. Crépy, T. Imamoto, G. Seidel, A. Fürstner, Organic Syntheses, 82, 22-29 (2005).
3. P-キラルホスフィン部位を有する環状金属錯体の合成と触媒活性，今本恒雄，化学工業, 55, 45-49 (2004).
4. セリウムを用いる有機合成反応，今本恒雄，第５班 実験化学講座 18巻；「有機化合物の合成VI（金属を用いる有機合成）」，村上正浩編，第２章,
2.8節 202–217 (2004).
(2) 卒業研究、大学院修士および博士論文修了指導人数（平成17年度）
卒業研究生 7 大学院修士論文 5 博士論文 0
(3) 国際会議出席と招待リスト
1. The 2005 International
Chemical Congress of
“New P-Chiral PhosphineLigands for Highly Enantioselective
Transition Metal-Catalyzed Reaction”
招待講演
2. 3rd Sino-Japanese Symposium on Organic Chemistry for Young
Scientists,
“New P-Chiral Phosphine Ligands: Their Design, Synthesis, and Application in Transition-Metal-Catalyzed Asymmetric Reactions”
招待講演
3. XX Congress of the International
“Structure and Sense
of Enantioselection of Rhodium Complexes of P-Chiral Diphosphines”
招待講演
4. The 13th Organometallic Chemistry Directed towards Organic
Synthesis,
“New P-Chiral Phosphine Ligands and Their Application in Transition Metal-Catalyzed Asymmetric Reactions”, Synthesis of Optically Pure P-Chiral (Dialkyl)arylphosphine-boranes via Nucleophilic Aromatic Substitution”, P-Vhiral o-Phosphinophenol as a P/O Hybrid Ligand: Preparation and Use in Cu-Catalyzed Asymmetric Conjugate Addition”
5. The 15th International Conference on Organic Synthesis,
2004年8月1日から8月6日
P-Stereogenic Bisphosphetane Ligands: Preparation and Use in
Rh-Catalyzed Asymmetric Hydrogenations, T. Imamoto, H. Takahashi, K. V. L.
Crépy, N. Oohara.
6. The 15th International Conference on Organic Synthesis,
2004年8月1日から8月6日
Synthesis and Use of P-Stereogenic P/O Hybrid Ligands
Y. Takahashi, H. Danjo, T. Imamoto
7.
Rare Earths ’04 in Nara, Japan, 2004 年11月7日から12日
Tandem Mass Spectrometric Analysis of Rare
Earth(III) Complexes: Evaluatio
of the Relative Strength of Their Lewis
Acidity
招待講演
(ア)
教育業績
なし
(5) 学会、国、県などへの協力など
1. 文部科学省 科学技術・学術審議会専門委員
2005年2月から2007年1月まで
2. The 21th IUPAC International Conference on Organometallic Chemistry,
2004, July,
3. OMCOS 14: Organometallic Chemistry Directed towards Organic Synthesis,
2007,
(イ)
特許
1. 2,3-ビス（ジアルキルホスフィノ）ピラジン誘導体及びその製造方法，並びに該誘導体を配位子とする金属錯体，発明者 今本恒雄，吉田和弘，杉田敬太郎，特許出願中，特願2005-215003
2. フェロセンを置換基に有する光学活性ホスフィン化合物およびそれらの遷移金属錯体の合成，発明者 大原宣彦，今本恒雄，特開2005-041867，公開日2005年2月17日
3. 新規光学活性リンキラルジホスフェタン化合物の製造方法，発明者 大原伸彦，今本恒雄WO
2005-010014，国際公開日2005年2月3日
なし