| Project/Area Number |
09440220
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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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 | Kyushu University |
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Principal Investigator |
KATSUKI Tsutomu Kyushu Univ., Fac. Sci., Professor, 大学院・理学研究科, 教授 (40037271)
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| Co-Investigator(Kenkyū-buntansha) |
IRIE Ryo Kyushu Univ., Fac. Sci., Res. Associate, 大学院・理学研究科, 助手 (70243889)
ITO Yoshio Kyushu Univ., Fac. Sci., Associate Professor, 大学院・理学研究科, 助教授 (00221086)
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| Project Period (FY) |
1997 – 1999
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| Project Status |
Completed (Fiscal Year 1999)
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| Budget Amount *help |
¥13,800,000 (Direct Cost: ¥13,800,000)
Fiscal Year 1999: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1998: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1997: ¥11,100,000 (Direct Cost: ¥11,100,000)
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| Keywords | asymmetric / ylide formation / (salen)cobalt / stepped conformation / (salen)manganese / hydroxylation / cyclopropanation / (salen)ruthenium / 不斉ヒドロキシル化 / CH-π / サレンマンガン錯体 / 不斉エポキシ化 / 速度論的分割 / 分子状酵素 / 不斉ヒドロキシル化反応 / サレン-マンガン錯体 / 不斉(2,3)-Wittig転位 / 非平面構造 / サレンコバルト錯体 / 触媒的不斉[2,3]Wittig転位 |
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| Research Abstract |
Metallosalen Complexes are excellent catalysts for asymmetric oxene and carbene transfer reactions but our understanding of the mechanism of asymmetric induction is still immature. However, knowledge on the mechanism is indispensable for understanding the stereochemistries of the asymmetric reactions and developing new type of highly efficient asymmetric reactions.
Although salen ligand had been recognized to have a planar structure, the analysis of stereochemistry in the ylide formation of sulfide using chiral (salen)cobalt complex suggested that the salen ligand had not a planar but stepped structure. This finding on the ligand-conformation was strongly supported by realizing as asymmetric epoxidation with achiral (salen)manganese complexes as catalysts in the presence of chiral axial ligands. Furthermore, X-ray analysis of chiral (salen)manganese complexes proved that the salen ligands adopt stepped conformation. Basing on these findings, we succeeded in an efficient kinetic resolution of allene compounds and asymmetric hydroxylation of benzylic C-H bonds.
In addition to these results, unique asymmetric cyclopropanation was also developed by employing nitroso (salen) ruthenium complexes. Though the ruthenium complexes are catalytically inactive, photo-irradiation makes them active. Furthermore, the complexes are expected to have highly pliable structure basing on the X-ray analysis of the complex. Taking advantage of high pliability of the ruthenium complex, we could controlled the ligand conformation by choosing solvent and achieve for the first time highly cis- and enantio-selective cyclopropanation.
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