CAS: 538-90-9; 2-(Prop-1-Enyl)Piperidine

📜5,6-octadienylamine置于[me2Si(η5-Me4C5)(T-Bun)]U(Nme2)2体系中,用 氘代苯 作为反应溶剂,化学反应生成 2-[(1Z)-1-丙烯-1-基]哌啶
参考文献:Constrained Geometry Organoactinides As Versatile Catalysts For The Intramolecular Hydroamination/cyclization Of Primary And Secondary Amines Having Diverse Tethered C−c Unsaturation
标题:Constrained Geometry Organoactinides As Versatile Catalysts For The Intramolecular Hydroamination/cyclization Of Primary And Secondary Amines Having Diverse Tethered C−c Unsaturation
摘要:A Series Of "Constrained Geometry" Organoactinide Complexes,(Cgc)An(Nme)(2) (Cgc = Me2Si(Eta(5)-Me4C5)((Bun)-Bu-T); An = Th,1; U,2),Has Been Prepared Via Efficient In Situ,Two-Step Protodeamination Routes In Good Yields And High Purity. Both 1 And 2 Are Quantitatively Converted To The Neutrally Charged,Solvent-Free Dichlorides (1-Cl-2,2-Cl-2) And Slightly More Soluble Diiodides (1-I-2,2-I-2) With Excess Me3Si-X (X = Cl,I) In Non-Coordinating Solvents. The New Complexes Were Characterized By NMR Spectroscopy,Elemental Analysis,And (For 1 And 2) Single-Crystal X-Ray Diffraction,Revealing Substantially Increased Metal Coordinative Unsaturation Vs The Corresponding Me2Sicp ''(2)Anr(2) (Cp '' = Eta(5)-Me4C5; An = Th,R = Ch2(Sime3),3; An = U,R = Ch2Ph,4) And Cp'(2)Anr(2) (Cp' = Eta(5)-Me5C5 ; An = Th,R = Ch2(Sime3),5; An = U,R = Ch2(Sime3),6) Complexes. Complexes 1-6 Exhibit Broad Applicability For The Intramolecular Hydroamination Of Diverse C-C Unsaturations,Including Terminal And Internal Aminoalkenes (Primary And Secondary Amines),Aminoalkynes (Primary And Secondary Amines),Aminoallenes,And Aminodienes. Large Turnover Frequencies (N-T Up To 3000 H(-1)) And High Regioselectivities (>= 95%) Are Observed Throughout,Along With Moderate To High Diastereoselectivities (Up To 90% Trans Ring Closures). With Several Noteworthy Exceptions,Reactivity Trends Track Relative 5F Ionic Radii And Ancillary Ligand Coordinative Unsaturation. Reactivity Patterns And Activation Parameters Are Consistent With A Reaction Pathway Proceeding Via Turnover-Limiting Cc/cc Insertion Into The An-N Sigma-Bond.
DOI:10.1021/ja0665444