| Project/Area Number |
17550045
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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 | Kyoto Pharmaceutical University |
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Principal Investigator |
UEMURA Motokazu Kyoto Pharmaceutical University, Visiting Professor, 薬学部, 客員教授 (90047241)
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| Co-Investigator(Kenkyū-buntansha) |
KAMIKAWA Ken Osaka Prefecture University, Faculty of Science, Asociate Professor, 理学系研究科, 助教授 (40316021)
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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 |
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 2005: ¥2,400,000 (Direct Cost: ¥2,400,000)
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| Keywords | arene chromium complex / Fischer carbene complex / planar chirality / axial chirality / asymmetric Heck reaction / Suzuki coupling / フィッシャーカルベン錯体 / 不斉Heck反応 / Suzukiカップリング / 面不斉アレーン金属錯体 / カルベン錯体 / 環化反応 |
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| Research Abstract |
We have developed asymmetric reactions by utilizing planar chiral arene transition metal complexes. Prochiral 2,6- dibutenylchrorobenzene chromium complex was subjected intramolecular asymmetric Heck reaction by treatment with chiral palladium(0) catalyst to give optical active indene chromium as planar chiral chromium complex. Furthermore, tandem asymmetric Heck reaction followed by Suzuki-Miyaura cross coupling with arylboronic acid gave optically active indane chromium complex.
Binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes were reacted with alkynes gave optically active cycloheptatriene chromium complexes via [3+2+2]-cycloaddition with high diastereoselectivity.
Moreover, binuclear α,β-unsaturated Fischer carbene complexes with planar chiral arene chromium complexes gave α- allyl β-arylpropionates up to 97% ee by reaction with allyl alkoxide and subsequent photo-oxidative demetalation. The chiral hetero-binuclear tungsten carbene compl
… More
exes afforded anti α-allyl β-hydoxy β-arylpropionates as a major product up to 92/8 dr. The reaction products, α-allyl β-arylpropionates were derived by 1,3-M(CO)_5 shift and subsequent [3,3]-sigmatropic rearrangement.
N-Aryl indoles with axially chiral N-C bonds were synthesized by stereoselective nucleophilic substitution reactions of planar chiral arene chromium complexes. Stereoselective chromium tricarbonyl migration was achieved in the sterically hindered N-ary indole chromium complex by refluxing in aromatic solvent.
Planar chiral arene chromium complexes with enyne bond were catalyzed by Au(I) catalyst to give axially chiral biaryl chromium complexes by cycloisomerization reactions. The obtained axially chiral biaryl chromium complexes are thermodynamically stable anti-complexes. These anti-biaryl chromium complexes are significant useful, since we have already reported that Suzuki-Miyaura cross coupling of planar chiral aryl bromide chromium complexes with arylboronic acids produced syn-biaryl chromium compresses. Less
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