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New Aspect on the Chemistry of Allenes

艾伦化学的新观点

基本信息

批准号：
16390005
负责人：
MUKAI Chisato
金额：
$ 9.54万
依托单位：
Kanazawa University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2006
项目状态：
已结题

项目摘要

This program has been directed toward development of efficient and novel reactions based on the inherent property of allenes, in particular, the allene possessing an electron-withdrawing group such as a phenylsulfonyl group. As a result, the following several reactions could be developed.(1) Treatment of 1-phenylsulfonylallene with a proper (co-hydroxy) alkyl side chain at the C,-position with a base afforded the corresponding oxacycles through the endo-mode cyclization process. This novel ring-closing reaction could be applied for the construction of five-to nine-membered oxacycles. The aza-congeners as well as carbocycles were also found to be prepared according to the standard conditions, thus developed. The sulfoxide, phosphine oxide, phosphonate, and ester functionalities were used as an electron-withdrawing group instead a sulfonyl moiety. Furthermore, allenylaniline derivatives provided the corresponding 2,3-disubstituted indoles in an endo-mode ring-closing manner. The allenyla … More niline having a hydroxymethyl group was converted into the indole-2,3-quinodimethane derivative via the intramolecular SN2' reaction.(2) The Pauson-Khand reaction of allenynes in the presence of Rh catalyst resulted in the efficient formation of bicyclo[4.3.0] as well as bicyclo[5.3.0] skeletons, the latter of which could not be prepared by the Pauson-Khand reaction of enynes. This new-type of Pauson-Khand reaction furnished the bicyclo[6.3.0] framswork as well. Alternatively, the carbodlimide functionality, which is isoelectronic to the allene group, could be successfully used in the Pauson-Khand reaction leading to the efficient construction of pyrrolo[2,3-b]indo1-2-ones.(3) Reaction of ene-bisallenes, generated from the corresponding propargyl alcohols, underwent the 6π-electrocyclic reaction to afford the quinodimethanes, which were susceptible to the [4+2]cycloaddition reaction with dienophiles. This novel method for the generation of quinodimethane species could be applied for the production of the naphthoquinodimethanes from benzene-bridged bisallene. Interestingly enough, the proper choice of the conditions in the step of bis-allene formation produced the cyclobutene derivatives instead of the [4+2]cycloadducts even if the suitable dienophiles were in existence. Less

该计划旨在开发基于联烯的固有性质的高效和新颖的反应，特别是具有诸如苯磺酰基的吸电子基团的联烯。结果如下：(1)1-苯基磺酰基烯在C-位带有适当的(共羟基)烷基侧链与碱基反应，通过内模环化反应得到相应的草环。这种新型的闭环反应可以应用于五元至九元氧杂环的构建。氮杂同系物以及碳环也被发现是按照标准条件制备的，从而开发了。亚砜、氧膦、膦和酯的官能团被用作吸电子基团，而不是磺酰基。此外，烯丙基苯胺衍生物以内模闭环的方式提供了相应的2，3-二取代吲哚。Alenyla…更多的含羟甲基的苯胺通过分子内SN2‘反应转化为吲哚-2，3-奎诺二甲烷衍生物。(2)在Rh催化剂存在下，烯丙炔发生Pauson-Khandd反应生成双环[4.3.0]和双环[5.3.0]骨架，后者不能通过烯炔的Pauson-Khandd反应得到。这种新型的Pauson-Khandd反应也提供了Bibclo[6.3.0]框架。另外，与烯丙基团等电子的卡地利胺官能团可以成功地用于Pauson-Khandd反应，从而有效地构建了吡咯并[2，3-b]吲哚1-2-酮。(3)由相应的炔丙醇生成的烯-双烯丙烯经过6π-电环反应得到了奎诺二甲烷，这对与双烯烃的[4+2]环加成反应很敏感。该新方法可用于由苯桥联双烯制取萘基喹二甲烷。有趣的是，在双烯丙烯形成步骤中适当选择条件，即使存在合适的亲二烯基团，也会生成环丁烯衍生物，而不是[4+2]环加合物。较少

项目成果

期刊论文数量（10）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

Studies of ring-closing mode of 4-hydroxy-2-vinylidenebutanoates: 5-exo-trig versus 5-endo-dig

DOI：
10.1016/j.tetlet.2007.01.037
发表时间：
2007-03
期刊：
Tetrahedron Letters
影响因子：
1.8
作者：
S. Kitagaki;D. Shibata;C. Mukai
通讯作者：
S. Kitagaki;D. Shibata;C. Mukai

Rh(I)-catalyzed Pauson-Khand reaction and cycloisomerization of allenynes: selective preparation of monocyclic, bicyclo[m.3.0], and bicyclo[5.2.0] ring systems.

DOI：
10.1021/jo050770z
发表时间：
2005-08
期刊：
The Journal of organic chemistry
影响因子：
0
作者：
C. Mukai;F. Inagaki;T. Yoshida;Katsuya Yoshitani;Yasuyuki Hara;S. Kitagaki
通讯作者：
C. Mukai;F. Inagaki;T. Yoshida;Katsuya Yoshitani;Yasuyuki Hara;S. Kitagaki

Norikazu Kuroda

黑田纪和