Catalytic Metal Enolization with a Single Metal Salt and Application to the Direct Enantioselective Aldol Reactions
| Project/Area Number |
17350049
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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 |
Synthetic chemistry
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| Research Institution | KYUSHU UNIVERSITY |
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Principal Investigator |
KANEMASA Shuji Kyushu University, Institute for Materials Chemistry and Engineering, Professor, 先導物質化学研究所, 教授 (20038590)
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| Co-Investigator(Kenkyū-buntansha) |
TANAKA Junji Kyushu University, Institute for Materials Chemistry and Engineering, Assistant, 先導物質化学研究所, 助手 (60155140)
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| Project Period (FY) |
2005 – 2006
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| Project Status |
Completed (Fiscal Year 2006)
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| Budget Amount *help |
¥14,800,000 (Direct Cost: ¥14,800,000)
Fiscal Year 2006: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2005: ¥11,100,000 (Direct Cost: ¥11,100,000)
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| Keywords | single metal salt / catalytic metal enolization / double catalytic activation / tolerant catalyst / Michael addition reaction / organocatalyst / nitro aldol reaction / diamine ether ligand / 触媒的金属エノラート化 / 環境調和型の製造プロセス / 求核剤前駆体のエノラート化 / 触媒的基質活性化手法 / 直接アルドール反応 |
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| Research Abstract |
The metal enolization catalyzed with a single metal salt was performed and the following results were obtained.
It was successful to develop a new double catalytic activation method in which a chiral Lewis activated both electrophiles and nucleophiles. The key for the success was (1) the use of cationic chiral Lewis acid catalysts and (2) the use of alcoholic medium in which the metal enolates catalytically formed were highly stabilized. It was needed to employ cationic chiral Lewis acid catalysts containing nickel(II) and cobalt(II) ions since these show tolerance toward strong nucleophiles. This catalytic metal enolization method was applied to enantioselective Michael addition reactions providing the development of a synthetic method of enantioselective and reactive reactions. This method enables the quaternary-quaternary carbon-carbon bond forming reactions including.
Chiral metal complex catalyststogether with a 1,2-ethanediamine were found to activate the catalyzed Michael addition reactions of substituted malononitriles and crotonaldehyde. This result shows that the additional 1,2-diamine ligand works as a ligand and also as an organocatalyst to brin about high rate acceleration.
The complex catalysts derived from diethylenetriamine ligand and cationic copper(II) salt was found to activate the nitroaldol reactions between nitromethane and a variety of aldehydes. With these promising results in hand, we synthesized several new chiral diamine ether ligands. The cationic nickel(II) complexes derived from these chiral ligands were found to give rise to excellent enantioselectivities in the direct asymmetric nitro aldol reactions.
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Report
(3 results)
Research Products
(15 results)
