Development of A New Cycloaddition Reaction Involving Azatrimethylenemethane Metal Complexes

详细研究了过渡金属催化氮杂甲基乙烷(ATMM) -钯的反应，并对部分ATMM-钯和-铂配合物的结构进行了表征。我们证明了4-亚甲基恶唑烷-2- 1(1)作为ATMM前体的效用。钯催化的4-亚甲基-3-芳基恶唑啉-2- 1 （1a）与降冰片烯的反应只产生环丙烷化产物，而4-亚甲基-3-芳基恶唑啉-2- 1 （1f-1）的反应主要产生环五环化产物。通过化学计量学和催化反应证实了atmm -钯[CH_2C (NR) CH_2] PdL_2的中间体作用。结果表明，在催化过程中中间体的异构化导致了环丙烷的生成。atmm -金属配合物的所有光谱数据表明，钯配合物具有接近eta^3模式的性质，对应的铂具有接近eta^2模式的性质。atmm -铂配合物的变温核磁共振研究表明，该配合物在溶液中具有eta^2配位模式的动态环皱化。用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的晶体数据：C_<46>H_<41>NO_2P_2SPt，三斜，a=15.635 (4) *, b=17.525 (5) *, C =11.126 (4) *, alpha=104.06 (3),beta=109.28 (2),gamma=66.56,P_1， Z=2。

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.