2007 Fiscal Year Final Research Report Summary
Research for Asymmetric Synthesis of Group 14-Element Centered Anions
| Project/Area Number |
18550044
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Organic chemistry
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| Research Institution | Tottori University |
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Principal Investigator |
NANJO Masato Tottori University, Department of Engineering, Associate Professor (50302352)
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| Project Period (FY) |
2006 – 2007
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| Keywords | germvllithium / silvllithium / stannvllithium / optically active / absolute structure / asymmetric synthesis |
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| Research Abstract |
Optically active organic germanium compounds bearing asymmetric germanium atom (methyl-1-naphtylphenylgermane and its derivatives) was previously reported by Brook et.al. However, far less attention has been devoted to optically active germyllithium or stannyllithium species. We report herein the results of a study of novel optically active germyllithium, using (-)-sparteine as a chiral ligand.
In the Schlenk tube, tert-butylmethylphenylgermyllithium (t-BuMePhGeLi) (1) was prepared by the reaction of the corresponding hydrogermane with tert-butyllithium in THF in the presence of half amounts of (-)-sparteine. The compound of 1 was characterized by ^1H, ^7Li and ^13C NMR spectra. The ligand-exchange reaction between 1-(sp) and 1-(THF)_2 was observed by variable-temperature NMR spectroscopy. The coalescence point was 107℃, and free energy of activation was calculated to be 18.0 kcal/mol. Optical resolution of germyllithium with (-)sparteine (1^*) was succeeded by recrystallization from n-
… More
hexane / toluene mixed solvent. The molecular structure of 1^* was determined by X-ray diffraction. As a result, absolute configuration of optically active 1^* was R configuration.
This method could also be applied to synthesis of optically active stannyllithium. Optical resolution of stannyllithium was succeeded by only addtion of half amount of (-)-sparteine into the racemic mixture of tert-butylmethylphenylstannyllithium (t-BuMePhSnLi) (2). The optically pure stannyllithium (-)-sparteine complex 2-(sp) was obtained as colorless crystals and its absolute structure had R configuration determined by X-ray crystallography.
In the presence of (-)-sparteine, tert-butylmethylgermane (t-BuMeGeH_2) was reacted with sec-butyllithium to give a (-)-sparteine complex of tert-butylmethylhydrogermyllithium (t-BuMeHGeLi, 3), quantitatively. 3-(sp) was added to triphenylchlorosilane to yield a coupling product of tert-butylmethyl (triphenylsilyll germane (t-BuMeHGeSiPh_3). The resulting optically active silylgermane shows 48%ee, and the absolute structure of the main product was determined by a single crystal X-ray diffraction to be S configuration. Less
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Research Products
(18 results)
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[Journal Article] Donor-Acceptor C_60-Containing Polyferrocenylsilanes: Synthesis, Characterization and Applications in Photodiode Devices2008
Author(s)
Masato, Nanio, Paul, W., Cyr, Kun, Liu, Edward, H., Sargent, Ian, Manners
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Journal Title
Advanced Functional Materials 18
Pages: 470-477
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Preparation, structural characterization, and reactivities of (digermanyl)lithium. Its application to the synthesis of bis(1,1-diphenyl-2,2,2-trimethyldigermanyl)-platinum(II)2007
Author(s)
Kunio, Mochida, Satoshi, Ogawa, Noriaki, Naito, Abd El-Al, Gabel, Usui, Yoko, Masato, Nanjo
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Journal Title
Chemistry Letters 36
Pages: 414-415
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Thermal Reactivity of cis- and trans-Bis(triphenylgermyl)bis(tertiaryphosphine)- platinum (II)2007
Author(s)
Kunio, Mochida, Takashi, Fukushima, Michiko, Suzuki, Wakako, Hatanaka, Mariko, Takayama, Yoko, Usui, Masato, Nanio, Kuniyoshi, Akasaka, Takako, Kudo, Sanshiro, Komiya
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Journal Title
Journal of Organometallic Chemistry 692
Pages: 395-401
Description
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[Journal Article] Synthesis and Kaleidoscopic Reactivities of Bis(tritolylgermyl)bis(dimethylphenyl-phosphine)platinum(II)2006
Author(s)
Yoko, Usui, Takashi, Fukushima, Masato, Nanjo, Kunio, Mochida, Kuniyoshi, Akasaka, Takako, Kudo, Sanshiro, Komiya
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Journal Title
Chemistry Letters 35
Pages: 810-811
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Synthesis of New Self-assembled Octahedrons Containing Group 14 Elements Dative Bonding of Pyrimidine Derivatives with Palladium Ions2006
Author(s)
Masato, Kazuhiko, Matsudo, Mari, Kurihara, Sayaka, Nakamura, Yoshio, Sakaguchi, Hisaharu, Hayashi, Kunio, Mochida
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Journal Title
Organometallics 25
Pages: 832-838
Description
「研究成果報告書概要(欧文)」より
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[Journal Article] Synthesis of New Self-assembled Octahedrons Containing Group 14 Elements Dative Bonding of Pyrimidine Derivatives with Palladium Ions2006
Author(s)
Yoshiyuki, Miura, Kanako, Ito, Seigo, Ohta, Keiko, Yano, Masato, Nanjo, Yoko, Usui, Kunio, Mochida
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Journal Title
Inorganic Chemistry Communications 9
Pages: 50-52
Description
「研究成果報告書概要(欧文)」より
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[Presentation] The Reaction of a Zerovalent Platinum Comlex with 1,2-Dihydrodisilane2007
Author(s)
Aki, Noda, Makiko, Takahashi, Mayumi, Yoshida, Hidekazu, Arii, Masato, Nanio, Kunio, Mochida
Organizer
54th Symposium on Organometallic Chemistry, Japan
Place of Presentation
Hiroshima university
Year and Date
20071027-28
Description
「研究成果報告書概要(欧文)」より
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[Presentation] Reactions of a Zerovalent Platinum Complex with 1,2-Dihydrodisilane2006
Author(s)
Masato, Nanjo, Aki, Noda, Motoaki, Nagano, Yoko, Usui, Kunio, Mochida
Organizer
53th Symposium on Organometallic Chemistry, Japan
Place of Presentation
Osaka City University
Year and Date
20060908-09
Description
「研究成果報告書概要(欧文)」より
