Development and Synthetic Application of Metalative Reppe Reaction
Development and Synthetic Application of Metalative Reppe Reaction
批准号:
14350472
负责人:
URABE Hirokazu
金额:
$4.03万
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B)
财政年份:
2002
资助国家:
日本
项目状态:
已结题
起止时间:
2002 至 2004
中文摘要
本研究开发了一种新型的Reppe反应,将三种不同的不对称乙炔作为钛化形式生成单一芳香化合物。或者,用腈取代上面的一个或两个乙炔,我们也开发了aza-Reppe反应,产生金属化吡啶或吡咯作为单个异构体。此外,这些新反应还制备了一些具有生物活性或药用价值的化合物。因此,由乙炔酯、末端乙炔、二价钛醇氧试剂(Ti(O-i-Pr)_4/2 i-PrMgCl(1))和丙炔溴作为单一异构体得到1)苄基钛化合物。这一反应被应用于第一次合成紫光色素A,并有效地合成了抗癌剂普拉地米星的芳香部分。2)α-吡啶基钛化合物是由乙炔酰胺、末端乙炔、钛试剂1和磺酰基腈组成的单一异构体。该反应用于合成抗过敏物质苯并环七吡啶。3)由乙炔酰胺、末端乙炔、钛试剂1和腈作为单一异构体得到吡啶乙醛。4)α-吡啶基钛化合物是由乙炔、腈、钛试剂1和磺酰基乙炔组成的单一异构体。从旋光性腈开始反应,我们得到了环噻唑霉素旋光性吡啶单元的有效制备。5)由乙炔、(磺胺)乙炔、钛试剂1和腈作为单一异构体得到氨基吡啶。6)由不对称乙炔、钛试剂1和两种不同的腈作为单一异构体得到了吡啶乙醛。
英文摘要
This research has developed new styles of the Reppe reaction, which afford single aromatic compounds as a titanated form from three different, unsymmetrical acetylenes. Alternatively, replacing one or two acetylene(s) above with nitriles, we also developed an aza-Reppe reaction, producing metalated pyridines or pyrroles as a single isomer. Moreover, some biologically active compounds or medicinally important compounds were prepared by these new reactions. Thus, 1)benzyltitanium compounds were obtained as a single isomer from acetylenic esters, terminal acetylenes, a divalent titanium alkoxide reagent (Ti(O-i-Pr)_4/2 i-PrMgCl (1)), and propargyl bromides. This reaction was applied to the first synthesis of alcyopterosin A and an efficient synthesis of an aromatic moiety of an anti-cancer agent, pradimicin. 2)α-Pyridyltitanium compounds were obtained as a single isomer from acetylenic amides, terminal acetylenes, the titanium reagent 1, and a sulfonylnitrile. This reaction was applied to the synthesis of an antiallergic substance, benzocycloheptapyridine. 3)Pyridinecarbaldehydes were obtained as a single isomer from acetylenic amides, terminal acetylenes, the titanium reagent 1, and nitriles. 4)α-Pyridyltitanium compounds were obtained as a single isomer from acetylenes, nitriles, the titanium reagent 1, and a sulfonylacetylene. Starting this reaction with optically active nitriles, we attained an efficient preparation of an optically active pyridine unit of cyclothiazomycin. 5)Aminopyridines were obtained as a single isomer from acetylenes, (sulfonylamino)acetylenes, the titanium reagent 1, and nitriles. 6)Pyrrolecarbaldehydes were obtained as a single isomer from unsymmetrical acetylenes, the titanium reagent 1, and two different nitriles.
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H.Urabe, D.Suzuki, F.Sato: "Generation of an Acetylene-titanium Alkoxide Complex. Preparation of (Z)-1,2-Dideuterio-1-(trimethylsilyl)-1-hexene"Org.Synth.. 80. 120-128 (2003)
H.Urabe、D.Suzuki、F.Sato:“乙炔-钛醇盐络合物的生成。(Z)-1,2-Dideuterio-1-(三甲基甲硅烷基)-1-己烯的制备”Org.Synth.. 80
DOI:
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发表时间:
期刊:
影响因子:
--
作者:
[]
通讯作者:
Preparation of Heterocyclic Compounds via Group 4(Ti or Zr) Metallacycles. Cyclization of, Acetylenes, Olefins, and Hetero-unsaturated Compounds
通过第 4 族(Ti 或 Zr)金属环制备杂环化合物。
DOI:
--
发表时间:
2005
期刊:
J.Synth.Org.Chem.Jpn. 63
影响因子:
--
作者:
[H.Urabe]
通讯作者:
H.Urabe
4族(Ti,Zr)メタラサイクルを経るヘテロ環化合物の合成法-アセチレン、オレフィン、およびヘテロ不飽和化合物の環化反応
通过第 4 族 (Ti,Zr) 金属环合成杂环化合物 - 乙炔、烯烃和杂不饱和化合物的环化反应
DOI:
--
发表时间:
2005
期刊:
有機合成化学協会誌 63
影响因子:
--
作者:
[A.Matsumoto, D.Furukawa, Y.Mori, T.Tanaka, K.Oka, 占部弘和]
通讯作者:
占部弘和
DOI:
10.1021/ja027008o
发表时间:
2002-08-21
期刊:
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
影响因子:
15
作者:
[Tanaka, R, Nakano, Y, Sato, F]
通讯作者:
Sato, F
DOI:
10.1002/chin.200331041
发表时间:
2003-04
期刊:
Journal of the American Chemical Society
影响因子:
15
作者:
[H. Urabe;D. Suzuki;Misa Sasaki;F. Sato]
通讯作者:
H. Urabe;D. Suzuki;Misa Sasaki;F. Sato
共 16 条
Efficient Nucleophilic Addition to Haloacetylenes and Its Application
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批准号:22655014
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项目类别:Grant-in-Aid for Challenging Exploratory Research
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资助金额:$2.19万
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财政年份:2010
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负责人:URABE Hirokazu
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依托单位:
New Synthetic Methods Based on Iron Catalysts
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批准号:21350027
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$11.23万
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财政年份:2009
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负责人:URABE Hirokazu
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依托单位:
Tandem cyclization based on titanium cascade-Development of short-step synthesis of optically active polycyclic compounds
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批准号:11650886
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$1.98万
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财政年份:1999
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负责人:URABE Hirokazu
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依托单位:
Practical Cyclization of Carbon-Carbon Multiple Bonds with Titanium (II) Reagent. -Application and Extension to Asymmetric Synthesis
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批准号:08651020
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项目类别:Grant-in-Aid for Scientific Research (C)
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资助金额:$1.15万
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财政年份:1996
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负责人:URABE Hirokazu
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依托单位: