Development of an efficient method for synthesizing N-heterocyclic compounds based on a divalent titanium complex
Development of an efficient method for synthesizing N-heterocyclic compounds based on a divalent titanium complex
批准号:
09555284
负责人:
SATO Fumie
金额:
$3.01万
依托单位国家:
日本
项目类别:
Grant-in-Aid for Scientific Research (B)
财政年份:
1997
资助国家:
日本
项目状态:
已结题
起止时间:
1997 至 1999
中文摘要
一种新的钛复合体(β I-D12-D1-丙烯)Ti(O-i-Pr)Ti D24-D2,与2 equiv的i-PrMgX (X = Cl或Br),作为一种通用钛(II)相等以影响后续独特的转变。因此, alkynes反应1对alkyne-titanium类型的复合体(β y D12 y D1-alkyne)Ti(O-i-Pr)alkynes D22 y D2,可以作为一种有机乙烯基dianion等价物在各种电磁药的反应中使用。酰亚胺和芦荟钛可以准备好从酰亚胺或丙酰亚胺衍生物通过1个氧化物添加途径的反应。当乙酰酯类在内核化学乙酰基取代(INAS)中得到的反应对afford α、β-不饱和碳基化合物、olefinic酯类Unergo Tandem INAS和内核碳基添加反应对给予环丙烷的反应。Ene-ene、ene-yne和yne-yne偶联反应发生在一个内部或内分子方式中,以及通过一个化学-、regio-、立体声方式中的不同电泳反应中,通过合成N-异环和/或他们的前体,其中包括五聚氰胺、幽门螺杆菌、印度元、光学活性N-异环、2,6-干扰性吡啶、β-乳糖、氮杂素和γ-氨基碳基化合物。
英文摘要
A new titanium complex (ηィイD12ィエD1-propene)Ti(O-i-Pr)ィイD22ィエD2 (1), generated in situ by treatment of Ti(O-i-Pr)ィイD24ィエD2 with 2 equiv of i-PrMgX (X = Cl or Br), nicely acts as a versatile titanium(II) equivalent to effect the following unique transformations. Thus, alkynes react with 1 to afford the alkyne-titanium complexes of type (ηィイD12ィエD1-alkyne)Ti(O-i-Pr)ィイD22ィエD2, which could be utilized as a vicinal vinylic dianion equivalent in the reactions with various kinds of electrophiles. Allyl- and allenyltitaniums could readily be prepared from allylic or propargylic alcohol derivatives by the reaction with 1 through an oxidative addition pathway. While acetylenic esters resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford α,β-unsaturated carbonyl compounds, olefinic esters undergo tandem INAS and intramolecular carbonyl addition reactions to give cyclopropanols. Ene-ene, ene-yne, and yne-yne coupling reactions proceed in an intra- or intermolecular way via a cyclometallation reaction, and the generated titanacyclic complexes react with a variety of electrophiles in a chemo-, regio-, stereoselective way.By utilizing these reactions, we have now succeeded in synthesizing N-heterocycles and/or their precursors, which include quinolones, pyrroles, indoles, optically active N-heterocycles, 2,6-disubstituted piperodines, β-lactams, azasugars and γ-amino carbonyl compounds.
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Hirokazu Urabe: "A Titanacycle-to-Carbocycle Relay Leading to an Expedient Synthesis of Cycleopentadienols"Angew. Chem. Int. Ed. Engl. 39, 23. 3516-3518 (1999)
Hirokazu Urabe:“钛环到碳环的中继导致环戊二烯醇的便捷合成”Angew。
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通讯作者:
Hirokazu Urabe: "A Titanacycle-to-Carbocycle Relay Leading to an Expedient Synthesis of Cyclopentadienols"Angew. Chem. Int. Ed. Engl.. 39, 23. 3516-3518 (1999)
Hirokazu Urabe:“钛环到碳环的中继导致环戊二烯醇的便捷合成”Angew。
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通讯作者:
Hirokazu Urabe: "Stereocontrolled Cyclization of Enynols and Allenynols with (η^2-Propene)Ti(O-i-Pr)_2 Important Role of Unprotected Hydroxy Group at a Remote Position" Tetrahedron Letters:. 39,40. 7329-7332 (1998)
Hirokazu Urabe:“烯醇和烯醇与 (η^2-丙烯)Ti(O-i-Pr)_2 远程位置上未受保护的羟基的重要作用”四面体快报:39,40 (1998)。
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Xin Teng: "Synthesis of Chiral Allyltitaniums Having an Amino Group at the C-4 Position and Their diastereoslective Addition Reaction with Aldehydes"Tetrahedron Letters. 38, 52. 8977-8980 (1997)
滕鑫:“C-4位氨基手性烯丙基钛的合成及其与醛的非对映加成反应”四面体快报。
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作者:
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通讯作者:
Hirokazu Urabe: "A Titanacycle-to-Carbocycle Relay Leading to an Expedient Synthesis of Cyclopentadienols"Angew. Chem. Int. Ed. Engl. 39,23. 3516-3518 (1999)
Hirokazu Urabe:“钛环到碳环的中继导致环戊二烯醇的便捷合成”Angew。
DOI:
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发表时间:
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影响因子:
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作者:
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共 32 条
Practical synthetic methodology using a divalent titanium compound
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批准号:15350054
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项目类别:Grant-in-Aid for Scientific Research (B)
-
资助金额:$9.22万
-
财政年份:2003
-
负责人:SATO Fumie
-
依托单位:
Practical Synthetic Reactions for Tine Chemical Using a Divalent Titanium Reagent
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批准号:12450359
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$10.05万
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财政年份:2000
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负责人:SATO Fumie
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依托单位:
Direct synthetic method for preparation of organotitanium complexes and their synthetic utility
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批准号:07455359
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项目类别:Grant-in-Aid for Scientific Research (B)
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资助金额:$4.61万
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财政年份:1995
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负责人:SATO Fumie
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依托单位:
Development of practical synthetic method for preparation of alcohols in chiral from.
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批准号:05650871
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项目类别:Grant-in-Aid for General Scientific Research (C)
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资助金额:$1.34万
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财政年份:1993
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负责人:SATO Fumie
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依托单位:
Development of a General Method for Synthesis of Optically Active Tertiarv Allylic Alcohols and Its Applications
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批准号:02453091
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项目类别:Grant-in-Aid for General Scientific Research (B)
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资助金额:$3.46万
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财政年份:1990
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负责人:SATO Fumie
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依托单位:
Acyclic stereoselection using 1, 2-diastereoselective induction reactions
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批准号:62550623
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项目类别:Grant-in-Aid for General Scientific Research (C)
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资助金额:$1.6万
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财政年份:1987
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负责人:SATO Fumie
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依托单位: