Development of Highly Efficient Methods for the Construction of Carbon Frameworks Utilizing Titanium-Carbene Complexes
Development of Highly Efficient Methods for the Construction of Carbon Frameworks Utilizing Titanium-Carbene Complexes
批准号:
11440213
负责人:
TAKEDA Takeshi
金额:
$8.83万
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B)
财政年份:
1999
资助国家:
日本
项目状态:
已结题
起止时间:
1999 至 2001
中文摘要
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英文摘要
In this study, new methods for the construction of fundamental carbon frameworks utilizing titanium-carbene complexes, prepared by the desulfurizarion of thioacetals with titanocene(II) species, were explored.1. Intermolecular reactions of titanium-carbene complexesThe reaction of carbene complexes with nitriles proceeded via the formation of azatitariacyclobutene to produce acylation products in good yields. The treatmant of vinylcarbene complexes with tert-halides gave the vinyltitanium species, which reacted with terminal alkynes and aldehydes to produce the corresponding adducts. Various allylsilanes were prepared by the reaction of the carbene complexes generated from 1,3-bis(phenylthio)propenes possessing a trialkylsilylmethyl group.2. Intramolecular reactions of titanium-carbene complexesThioacetals bearing a carbon-carbon double bond afforded the unsaturated cyclic compounds via the ring-closing metathesis process when being treated with titanocene(II) species. This reaction wa … More s successfully applied to the synthesis of various heterocycles such as cyclic amines, ethers, and sulfides. The ring-closing metathesis and subsequent oxidative cleavage of unsaturated thioacetals possessing a silyl ether moiety gave the Z-1 ,5-olefmic diols with high stereoselectivity. It was found that the esters and thiolesters bearing a thioacetal moiety were good substrates for the intramolecular carbonyl olefination giving a variety of unsaturated cyclic compounds. Using this method, regioselective preparation of enol ethers of cyclic ketones, synthesis of dihydrothiophenes, and transformation of carboxylic acids into o-hydroxy ketones have been achieved.3. Reaction of organotitanium species generated from organic halides and titanocene(II)The treatment of gem-dihalides having a terminal carbon-carbon double bond with the titanocene(II) species produced the bicyclic cyclopropanes. The 1,2-disubstituted cyclopropanes were also produced with high trans-selectivity by the reaction of 1,3-dihalides with the titanocene(II) reagent. Less
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Takeshi Takeda: "Titanocene(II)-Promoted Desulfurizative Acylation of Thioacetals with Alkanenitriles"Tetrahedron Lett.. 41-1. 65-68 (2000)
Takeshi Takeda:“二茂钛 (II)-促进硫代缩醛与烷腈的脱硫酰化”Tetrahedron Lett.. 41-1。
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Tooru Fujiwara: "Titanocene(II)-Promoted Ring-Closing Metathesis of Thioacetals Having a carbon-Carbon Double Bond"Tetrahedron : Synposia -in-print. 56-28. 4859-4869 (2000)
Toru Fujiwara:“二茂钛 (II) 促进的具有碳-碳双键的硫缩醛的闭环复分解”四面体:概要 - 印刷中。
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Md.Abdur Rahim: "Titanocene(II)-Promoted Olefination of ω,ω-Bis(phenylthio)alkyl Alkanoates. A New Method for the Preparation of ω-Hydroxy Ketones"Tetrahedron. 56-5. 763-770 (2000)
Md.Abdur Rahim:“二茂钛 (II) 促进的 ω,ω-双(苯硫基)烷基链烷酸酯的烯化。制备 ω-羟基酮的新方法”Tetrahedron 56-770 (2000)。
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Takeshi Takeda: "Synthesis of Carbo- and Hetero-cycles by the Titanocene(II)-Promoted Reactions of Thioacetals"Polyhedron : Synposia-in-print. 19-5. 593-596 (2000)
Takeshi Takeda:“通过二茂钛 (II) 促进的硫缩醛反应合成碳环和杂环”多面体:印刷中的概要。
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通讯作者:
Takeshi Takeda: "Titanocene(II)-Promoted Olefination of ω,ω-Bis(phenylthio)alkyl Alkanoates. A New Method for the preparation of ω-Hydroxy Ketones"Tetrahedron. 56・5. 763-770 (2000)
Takeshi Takeda:“二茂钛 (II) 促进 ω,ω-双(苯硫基)烷基链烷酸酯的烯化。制备 ω-羟基酮的新方法”Tetrahedron 56・5 (2000)。
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共 31 条
Highly Stereocontrolled Construction of Acyclic Systems Utilizing Titanocene Complexes as Synthetic Devices
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批准号:21350026
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$12.4万
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财政年份:2009
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负责人:TAKEDA Takeshi
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依托单位:
Formation of Titanium-Metallacycles and Exploration of Their Reactivities
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批准号:18350018
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$9.56万
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财政年份:2006
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负责人:TAKEDA Takeshi
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依托单位:
Exploration of Unique Reactivity of Organotitanocene Complexes and Its Application to Organic Synthesis
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批准号:14340228
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$8.26万
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财政年份:2002
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负责人:TAKEDA Takeshi
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依托单位:
Development of New oxidation Processes Utilizing New Low toxic Oxidizing Agent "Bromocopper (II) t-butoxide"
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批准号:07555277
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项目类别:Grant-in-Aid for Scientific Research (A)
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资助金额:$5.25万
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财政年份:1995
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负责人:TAKEDA Takeshi
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依托单位:
海外基金