New Aspect on the Chemistry of Allenes

该计划旨在基于烯的固有性质，特别是具有吸电子基团（如苯基磺酰基）的烯，开发高效和新颖的反应。因此，可以产生以下几种反应。(1) 1-苯基磺酰基allene在C，-位置有一个合适的（共羟基）烷基侧链，带一个碱，通过内模环化过程得到相应的氧环。这种新颖的合环反应可用于构建五元至九元的氧环。在标准条件下还制备了偶氮同系物和碳环，并进行了开发。亚砜、氧化膦、膦酸盐和酯官能团被用作吸电子基团而不是磺酰基。此外，烯丙苯胺衍生物以模内闭合环的方式提供相应的2,3-二取代吲哚。带羟基的烯基苯胺通过分子内SN2′反应转化为吲哚-2,3-喹诺二甲烷衍生物。(2)在Rh催化剂的存在下，烯炔的Pauson-Khand反应可以有效地生成双环[4.3.0]和双环[5.3.0]骨架，而后者是烯炔的Pauson-Khand反应所不能制备的。这种新型的pason - khand反应也提供了脚踏车[6.3.0]的框架。或者，与烯基等电子的碳脲官能团可以成功地用于Pauson-Khand反应，从而有效地构建吡咯[2,3-b]吲哚1-2- 1。(3)由丙炔醇生成的烯-二烯通过6π电环反应生成醌二甲烷，醌二甲烷易与亲二酚发生[4+2]环加成反应。该新方法可用于苯桥二烯制萘醌二甲烷。有趣的是，即使存在合适的亲二烯试剂，在双烯形成步骤中适当选择条件也会产生环丁烯衍生物，而不是[4+2]环加合物。少

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