Insertion of Unsaturarel Organic Compounds into Carbon-Carbon Bonds

将不饱和有机化合物插入碳-碳键

• 批准号: 12450362
• 负责人: MURAKAMI Masahiro
• 金额: $ 9.66万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-12450362/
• 关键词: rhodium; cyclobutanone; carbon-carbon bond; eight-membered ring ketone; metallacycle; olefin insertion; decarbonylation; 8員環; 炭素-炭素結合切断; ローダサイクル; 挿入反応

Rhodium(I)-catalyzed intramolecular olefin insertion reactions of o-Styryl-substituted cyclobutanones were studied. When 3-(o-Styryl)cyclobutanone (1) was heated in m-xylene in the presence of a catalytic amount of Rh(I)-DPPE (Ph_2P(CH_2)_nPPh_2,n = 2) complex, 4-(o-styryl)-3-buten-2-one was obtained in 51% yield. The reaction of 1 in the presence of Rh(I)-DPPP (n=3) complex afforded benzobicyclo[3.2.1]octan-3-one in 81% yield. Decarbonylation of 1 occurred in the presence of Rh(I)-DPPB (n=4) complex to give 1-isopropenyl-2-vinylbenzene in 93% yield. 2-(o-Styryl)cyclobutanone underwent intramolecular olefin insertion reaction in the presence of Rh(I)-P(o-MeOC_6H_4)_3 complex to furnish eight-membered ring unsaturated ketones in 75% yield.

研究了铑催化邻苯乙烯基取代环丁酮的分子内烯烃插入反应。在催化量的Rh（I）-DPPE（Ph_2P（CH_2）_nPPh_2，n = 2）络合物存在下，在间二甲苯中加热3-（邻苯乙烯基）环丁酮（1），得到4-（邻苯乙烯基）-3-丁烯-2-酮，产率51%。1在Rh（I）-DPPP（n=3）配合物存在下反应得到苯并双环[3.2.1]辛-3-酮，产率81%。1在Rh（I）-DPPB（n=4）配合物存在下脱羰基得到1-异丙烯基-2-乙烯基苯，产率93%。2-（邻苯乙烯基）环丁酮在Rh（I）-P（o-MeOC_6 H_4）_3络合物存在下发生分子内烯烃插入反应，得到八元环不饱和酮，产率75%。