Novel Synthesis of 5 and 6-membered Cyclic Ketones by Highly selective Photoaddition Reactions of Acylgermanes

酰基锗烷高选择性光加成反应新合成 5 元和 6 元环酮

• 批准号: 02640397
• 负责人: KIYOOKA Syun-ichi
• 金额: $ 1.34万
• 依托单位: Kochi University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (C)
• 财政年份: 1990
• 资助国家: 日本
• 起止时间: 1990 至 1991
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-02640397/
• 关键词: Organogermanium; Cyclic Ketone Synthesis; Photoaddition; Organic Synthesis; 5員環および6員環ケトン; アシルゲルマン; 光環化反応; βーゲルミルケトン

There has been rapid development of a large number of remarkable organic reactions with functionalized silicon reagents. In contrast, development of germanium chemistry has been quite restricted. The utilization of organogermanium compounds in organic synthesis has begun to generate considerable interest. The photochemical reactions characteristic of acylgermanes can be of interest as a novel means of generating acyl radicals. Acylgermanes are useful photoprecursors to acyl radicals and can be used in the synthesis of novel cyclic ketones having germyl groups.The photochemical intramolecular cyclization reactions of acylgermanes proceed efficiently. In conclusion 5-exo-trig and 6-exo-trig modes of cyclization are apparently favored in these photochemical intramolecular cyclization reactions of acylgermanes. The chemistry offers a novel and effective method for the 5 and 6-membered ring ketones.Some subsequential carbon-carbon bond formation reactions using the triphenylgermyl functionality in these reactions are being developed.

近年来，利用功能化硅试剂进行的大量引人注目的有机反应得到了迅速发展。相比之下，锗化学的发展受到相当大的限制。有机锗化合物在有机合成中的应用已开始引起人们的极大兴趣。酰基锗烷的光化学反应特性可以作为一种新的产生酰基自由基的手段。酰基锗烷是酰基自由基的前体，可用于合成含锗酰基的新型环状酮，其光化学分子内环化反应能有效地进行。因此，5-外消旋和6-外消旋环化模式在酰基锗烷的光化学分子内环化反应中是有利的。该化学为五元环酮和六元环酮的合成提供了一种新的有效的方法，利用三苯基锗基官能团的连续碳碳键形成反应正在发展之中。

项目成果

S.Kiyooka,Y.Kaneko,H.Matsue,M.Hamada: "Photochemical Intramolecular Cyclization Reactions of Acylgermanes" Journal of Organic Chemistry. 55. 5562-5564 (1990)

S.Kiyooka，Y.Kaneko，H.Matsue，M.Hamada：“酰基锗烷的光化学分子内环化反应”有机化学杂志。

S.Kiyooka,Y.Kaneko,H.Matsue,M.Hamada: "Photochemical Intramolecular Cyclization Reactions of Acylgermanes" Journal of Orgamic Chemistry. 55. 5562-5564 (1990)

S.Kiyooka，Y.Kaneko，H.Matsue，M.Hamada：“酰基锗烷的光化学分子内环化反应”有机化学杂志。

S. Kiyooka, Y. Kaneko, H. Matsue, M. Hamada, and R. Fujiyama: "Photochemical Intramolecular Cyclization Reactions of Acylgermanes" J. Org. Chem.55. 5562 (1990)

S. Kiyooka、Y. Kaneko、H. Matsue、M. Hamada 和 R. Fujiyama：“酰基锗烷的光化学分子内环化反应”J. Org。

Syunーichi Kiyooka,Yuichi Kaneko,and Hideaki Matsue: "Photochemical Intramolecular Cyclization of Acylgermanes" Journal of Organic Chemistry. 55. 5562-5564 (1990)

Syunichi Kiyooka、Yuichi Kaneko 和 Hideaki Matsue：“酰基锗烷的光化学分子内环化”有机化学杂志 55. 5562-5564 (1990)。