Dynamic Control of Stereochemistry in Carbon-Carbon and Carbon-Silicon Bonds Formations through Electron Transfer Reaction
| Project/Area Number |
10208205
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| Research Category |
Grant-in-Aid for Scientific Research on Priority Areas (B)
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| Allocation Type | Single-year Grants |
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| Research Institution | Nagaoka University of Technology |
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Principal Investigator |
NISHIGUCHI Ikuzo Nagaoka University of Technology, Faculty of Engineering ; Professor, 工学部, 教授 (20026347)
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| Co-Investigator(Kenkyū-buntansha) |
OHMORI Hidenobu Osaka University, Graduate School of Pharmacology ; Professor, 大学院・薬学研究科, 教授 (90028845)
NONAKA Tsutomu Turuoka National College of Technology ; Principle, 校長 (00016528)
MAEKAWA Hirofumi Nagaoka University of Technology, Faculty of Engineering ; Assistant Professor, 工学部, 助手 (70283041)
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| Project Period (FY) |
1998 – 2000
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| Project Status |
Completed (Fiscal Year 2001)
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| Budget Amount *help |
¥48,700,000 (Direct Cost: ¥48,700,000)
Fiscal Year 2000: ¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 1999: ¥16,100,000 (Direct Cost: ¥16,100,000)
Fiscal Year 1998: ¥16,500,000 (Direct Cost: ¥16,500,000)
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| Keywords | Electron transfer reaction / Stereoselective reaction / Magnesiun metal / Carbon-acylation / Carbon-silylation / Electroreduction / (Z)-α-Chloroglycidyl esters / Irradiation of ultrasounds / 環開裂反応 / ヘテロ環飽和化合物 / 還元的脱離反応 / オレフィンアルコール / 立体特異性 / 超音波照射 / 立体化学効果 / 高立体選択的 / 高位置選択的 / クマリン誘導体 / ジハイドロピリジン類 / 高立体選択性 / 分子内環化反応 / 炭素-炭素結合形成反応 / シス-ジアルキルピロリジノール / (Z)-クロログリシジルエステル / 反応性金属陽極 / 還元的クロスカップリング |
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| Research Abstract |
In this study, highly regio- and stereoselective carbon-carbon and carbon-silicon bonds formations, which cannot be observed in a homogeneous solution, have been developed through dynamic control of stereochemistry of reactive intermediates generated on a heterogeneous interface between solid and liquid by electron transfer reactions from metals or electrodes to organic compounds. For example, treatment of 3-alkylcoumarins as typical aromatic α,β-unsaturated esters with acid anhydrides in the presence of easily available Mg turning without any pre-treatment brought about highly regio- and stereoselective C-acylation to give the thermodynamically unfavorable cis-3-alky-4-acyldihydrocoumarins with stereo-selectivity of 92-98%. Under the similar reaction conditions, high regio- and stereoselectivities were also observed in the Mg-promoted silylation of 3-alkylcoumarins and dimethyl 1,2-dihydro-2,3-pyridinedicarboxylates.
On the other hand, (Z)- and (E)-3-buten-1-ols were exclusively obtained in the stereospecific manner from electroreductive ring-cleavage of cis- and trans- 2-substituted-3-chlorotetrahydrofurans, respectively. Furthermore, electroreduction of methyl trichloroacetate in the presence of aliphatic aldehydes using a reactive Zn anode resulted in stereoselective corss-coupling giving (Z)-α-chloroglycidyl esters. Also, remarkable stereoselectivity control by irradiation of ultrasounds onto the electorode surface was successfully established in the electroreductive dimerization of acetophenone and debromination of dl-1,2-dibromoethanes.
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Report
(4 results)
Research Products
(44 results)
