New synthesis of a seven member ring fused heterocycles using ring expansion reaction of an aromatic ring
Project/Area Number |
19590009
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Research Category |
Grant-in-Aid for Scientific Research (C)
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Allocation Type | Single-year Grants |
Section | 一般 |
Research Field |
Chemical pharmacy
|
Research Institution | Nagoya City University |
Principal Investigator |
AOYAMA Toyohiko Nagoya City University, 大学院・薬学研究科, 教授 (80080191)
|
Project Period (FY) |
2007 – 2009
|
Project Status |
Completed (Fiscal Year 2009)
|
Budget Amount *help |
¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2009: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000)
Fiscal Year 2008: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2007: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
|
Keywords | ヘテロ環化学 / トリメチルシリルジアゾメタン / アルキリデンカルベン / アリールアセチレン / アリールプロピオレート / ピロリジン / β-アミノケトン / アリール(オキソ)アセテート / インダゾール / [3+2]環化付加反応 / t-ブチル(2-メトキシフェニィル)(オキソ)アセテート / ベンゾフラン-3-カルボキシレート / Buchner反応 / 2-アザアズレン / 2-ジアゾ-2-トリメチルシリルエタノール / ピラゾール |
Research Abstract |
(1) Ketones reacted with magnesium bromide salt of trimethylsilyldiazomethane (TMSCHN_2) to give the corresponding 2-diazo-2-(trimethylsilyl)ethanols which were easily converted to pyraazoles by 1,3-dipole cycloaddition the reaction with acetylenes. (2) Aryl and heteroaryl aldehydes were easily converted to functionalized acetykenes in on-pot using lithium salt of TMSCHN_2. (3) TMSCHN_2 reacted with thiobenzoyl isocyanates to give the corresponding diazoketones which were converted to 2-azaazulenes by treatment with rhodium acetates. (4) Diazo(trimethylsilyl)methylmagnesium bromide smoothly reacted with t-butyl aryl(oxo)acetates to afford the corresponding arylpropiolates via alkylidenecarbene intermediates. (5) Diazo(trimethylsilyl)methylmagnesium bromide readily reacted with ketones and aldehydes to give 2-diazo-(2-trimethylsilyl)ethanoles which were efficiently converted to indazoles bearing a hydroxmethyl unit at 3-position by intermolecular [3+2]cycloaddition with benzynes. (6) Diazo(trimethylsilyl)methylmagnesium bromide reacted with (o-methoxyphenyl)(oxo)acetates to readily afford 2-unsubstituted benzofuran-3-carboxylates via oxonium ylides formed from the initially generated alkylidenecarbene intermediates. (7) Lithium trimethylsilyldiazomethane reacted with N-benzyl-β-aminoketones at -78℃in THF to give 3-substituted 1-benzyl-3-(trimethylsiloxy)pyrrolidines in moderate to good yields.
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Report
(4 results)
Research Products
(23 results)