Researches on the Effect of Spiro-Activation of Small Ring Compounds in Their Ring Cleavage Reactions.

小环化合物螺环活化对其开环反应影响的研究。

• 批准号: 01430005
• 负责人: NISHIDA Shinya
• 金额: $ 17.92万
• 依托单位: Hokkaido University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (A)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-01430005/
• 关键词: Spiro-activation of cyclopropane; Ring cleavage of small rings; Cycloaddition reactions; TCNE; Oxidation potential; Ionization potential; Cation radical; 04Nucleophilic attack of the nitrogen in the chyano group; スピロシクロプロパン; スピロ活性化効果; 転位反応; シクロ

In continuation of the study on spiro-activation of cyclopropanes, reactions of spiroindans, spiroindenes, spiroheptenes, and spiroheptadienes with TCNE were examined. Although the basic reaction courses were [pi2+pi2] and [pi2+sigma2] cycloaddition as those observed in the reactions of spirofluorene derivatives, varied reactions were observed to occur depending upon substituents on the substrates. One of the most interesting observation was that the reaction of 1, 1-dicyclopropylspiro [2.4] hepta-4, 6-diene with TCNE gave, in addition to the expected Diels-Alder adduct, an imine derivative, which should be produced after extensive rearrangement. Similar transformation was observed to occur also in the reactions of spiroindenes. Evidently, this should be one of the basic reactions to be considered when TONE was allowed to react with vinylcyclopropanes. The other interesting result was that oxidation potential as well as ionization potential of spiroheptanes and spiroheptenes were influenced by the substituents on the cyclopropane ring as expected, but those of spiroheptadienes were not subjected to the substituent effect. The results are of great interest with regard to the structure of five-membered unsaturated cation radicals. In addition to these studies, the stereochemistry of TCNE cycloaddition and the reaction of diphenyl-substituted spirofluorene derivatives were investigated. All results gave important basic knowledge with regard to the spiro-activation of cyclopropanes. Finally, it was found that even 1, 2-dicyclopropylethylene reacted with TCNE in the [pi2+sigma2] manner under certain reaction conditions. In relation to this result, the photochemical reaction of 1, 2-dicyclopropylethylene with chloranil was also examined. The results provided supporting evidences that the reaction involving cyclopropane cleavage might be characteristic to that of cation radical intermediates.

在环丙烷螺活化研究的继续中，检查了螺茚满、螺茚烯、螺庚烯和螺庚二烯与TCNE的反应。虽然基本反应过程是[pi2+pi2]和[pi2+sigma2]环加成，如在螺芴衍生物的反应中观察到的那些，但是根据底物上的取代基观察到发生不同的反应。最有趣的观察之一是，1, 1-二环丙基螺[2.4]庚-4, 6-二烯与 TCNE 的反应，除了预期的第尔斯-阿尔德加合物之外，还产生了亚胺衍生物，该衍生物应在广泛的反应后产生。重新排列。在螺茚的反应中也观察到类似的转变发生。显然，这应该是TONE与乙烯基环丙烷反应时要考虑的基本反应之一。另一个有趣的结果是，螺庚烷和螺庚烯的氧化电势和电离电势如预期一样受到环丙烷环上取代基的影响，但螺庚二烯的氧化电势和电离电势不受取代基的影响。该结果对于五元不饱和阳离子自由基的结构非常有意义。除了这些研究之外，还研究了 TCNE 环加成的立体化学和二苯基取代的螺芴衍生物的反应。所有结果都提供了有关环丙烷螺环活化的重要基础知识。最后发现即使是1,2-二环丙基乙烯在一定的反应条件下也能与TCNE以[pi2+sigma2]的方式反应。与该结果相关，还研究了1,2-二环丙基乙烯与四氯苯醌的光化学反应。结果提供了支持证据，表明涉及环丙烷裂解的反应可能是阳离子自由基中间体反应的特征。

项目成果

S. Nishida, N. Asanuma, T. Tsuji, and T. Imai: "Unique Thermal Isomerization of the Diels-Alder Adduct of 1, 1-Dicyclopropylspiro [2.4] hepta-4, 6-diene with TCNE." Chemistry Letters. 495-498 (1991)

S. Nishida、N. Asanuma、T. Tsuji 和 T. Imai：“1, 1-二环丙基螺[2.4]庚-4, 6-二烯与 TCNE 的 Diels-Alder 加合物的独特热异构化。”

S. Nishida, M. Murakami, T. Mizuno, and T. Tsuji: "Reactions of Some Cyclopropylethylenes with TCNE. A Remarkable Effect of Spiro-Activation in the Cycloaddition." Journal of Organic Chemistry. Vol. 54. 3868-3872 (1989)

S. Nishida、M. Murakami、T. Mizuno 和 T. Tsuji：“一些环丙基乙烯与 TCNE 的反应。环加成中螺环活化的显着效果。”

T. Tsuji, M. Ohkita, and S. Nishida: "pi-Facial Selectivity in Diels-Alder Reactions of [4.3.2] propella-2, 4, 8, 10-tetraen-7-one and Its Derivatives. Synthesis of 2, 5-Etheno [4.3.2] propella-3, 8, 10-trien-7-one." Journal of Organic Chemistry. Vol. 56.

T. Tsuji、M. Ohkita 和 S. Nishida：“[4.3.2] propella-2, 4, 8, 10-tetraen-7-one 及其衍生物的 Diels-Alder 反应中的 pi-Facial Selectivity。

S,Nishida,M.Muraーkami,T.Mizuno,and T.Tsuji: "Reactions of Some Cyclopropythylense with TCNE. A Remarkable Effect of SpiroーActivation in the Cycloaddiーtion." Journal of Organic Chemistry. 54. 3868-3872 (1989)

S、Nishida、M. Murakami、T. Mizuno 和 T. Tsuji：“某些环丙烷与 TCNE 的反应。SpiroActivation 在 Cycloload 饮食中的显着效果。有机化学杂志”54。3868-3872（1989）。

S. Nishida, M. Murakami, H. Oda, T. Tsuji, T. Mizuno, M. Matsubara, and N. Kikai: "Reactions of Some Cyclopropanes Activated by a Spiro-Linked Fluorene. Importance of Electronic Matching of a Reacting Partner in Thermal Cycloaddition with TCNE and Ring-Op

S. Nishida、M. Murakami、H. Oda、T. Tsuji、T. Mizuno、M. Matsubara 和 N. Kikai：“由螺环芴激活的一些环丙烷的反应。反应伙伴电子匹配的重要性