Development of A New Cycloaddition Reaction Involving Azatrimethylenemethane Metal Complexes

涉及氮杂三亚甲基甲烷金属配合物的新型环加成反应的开发

• 批准号: 07555287
• 负责人: MURAI Shinji
• 金额: $ 8.38万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1995
• 资助国家: 日本
• 起止时间: 1995 至 1996
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-07555287/
• 关键词: azatrimethylenemethane; cycloaddition; oxatrimethylenemethane; cyclopentanone; palladium; platinum; 環化付加反応; シクロプロパン

Transition-metal catalyzed reactions involving azatrimethylenemethane (ATMM) -palladium were investigated in detail, and structures of some ATMM-palladium and -platinum complexes were fully characterized. We demonstrated the utility of 4-methyleneoxazolidin-2-one (1) as a precursor of ATMM.The palladium-catalyzed reaction of 4-methylene-3-tosyloxazolidin-2-one (1a) with norbornenes exclusively gave a cyclopropanation product, while the reaction of 4-methylene-3-aryloxazilidin-2-one (1f-1) mainly produced a cyclopentaannulation product. The intermediacy of an ATMM-palladium, [CH_2C (NR) CH_2] PdL_2 was elucidated by the stoichiometric and catalytic reactions employing the isolated complex. The results shows that the isomerization of an intermediate during the catalytic process leads to the formation of the cyclopropanes. All spectral data of ATMM-metal complexes indicated that the palladium complexes have the nature close to eta^3-mode and the corresponding platinums to eta^2-mode. Variable temperature NMR studies on the ATMM-platinum complexe exhibited the dynamic ring-puckering with eta^2-coordination mode in a solution. The solid-state structures of [CH_2C (NTs) CH_2] Pt (PPh_3) _2 was confirmed by an X-ray crystallography. Crystal data for [CH_2C (NTs) CH_2] Pt (PPh_3) _2 at 25ﾟC : C_<46>H_<41>NO_2P_2SPt, triclinic, a=15.635 (4) *, b=17.525 (5) *, c=11.126 (4) *, alpha=104.06 (3) ﾟ,beta=109.28 (2) ﾟ,gamma=66.56ﾟ,P_1, Z=2.

详细研究了过渡金属催化反应涉及苯甲酰甲基甲烷（ATMM） - 甲基烷 - - 核酸甲烷（ATMM） - 甲基甲烷反应，并充分表征了某些ATMM -Palladium和-platinum复合物的结构。我们证明了4-甲基羟恶唑肽-2-one（1）作为ATM的前体。4-甲基3-甲基氧甲唑啉-2-酮（1A）与诺尔伯伦氏菌与荷苯甲酸盐与甲基苯甲酸盐的反应的palladium-cataliz-催化作用，独立于诺伯烯蛋白的反应，独有地给出了环孕产物的反应环载产物。 ATMM-甲基的中间体[CH_2C（NR）CH_2] PDL_2通过使用分离的复合物的化学计量和催化反应阐明了PDL_2。结果表明，催化过程中中间体的异构化导致了环丙烷的形成。 ATMM金属配合物的所有光谱数据均表明钯络合物的性质接近ETA^3模式，并且与ETA^2模式相应的铂。在AMP-Platinum复合物上进行的可变温度NMR研究在溶液中以ETA^2协调模式暴露了动态戒指。 X射线晶体学证实了[CH_2C（NTS）CH_2] PT（PPH_3）_2的固态结构。 [CH_2C（NTS）CH_2] pt（pph_3）_2 at 25 c：C_ <46> H__ <41> NO_2P_2SPT，Triclinic，A = 15.635（4） *，B = 17.525（5） *，C = 11.126（4）（4）（4） *10. 3.2， （2）ﾟ，伽马= 66.56 ﾟ，p_1，z = 2。