结果表明,在质子传递溶剂(如H 2 O. MeOH和EtOH)中,在H 2 SO 4存在下,辐照2-烯丙基化的苯胺(参见方案2-4、7和8)经历了新的光解反应特别地产生反式-2-羟基和反式-2-烷氧基-1-甲基茚满。中间体大概是在分子内[2 s + 2 s ]环加成反应中形成的三环[4.3.0.0 1,8 ] nona-2,4-二烯(参见方案7)。另一方面,N,N,N-三甲基-2-(1'-甲基烯丙基)苯胺盐18(方案6)和2-(3'-丁烯基)-N,N-二甲基苯胺(17)在MeOH或H 2 SO 4 / MeOH中辐射后,铵基还原生成(1-甲基烯丙基)苯(19)和1-甲基茚满(20)。
Ionic diamine rhodium complex catalyzed hydroaminomethylation of 2-allylanilines
摘要:
Ionic diamine rhodium complexes catalyze the hydroaminomethylation of 2-allylanilines. The reaction involves initial hydroformylation followed by reductive amination, which provides direct access to 1,2,3,4-tetrahydroquinolines and 2,3,4,5-1H-1-benzazepines. (C) 2010 Elsevier Ltd. All rights reserved.
High-valent Molybdenum Imido Complexes with Tethered Olefins
作者:Inke Siewert、Christian Limberg、Burkhard Ziemer
DOI:10.1002/zaac.200500508
日期:2006.5
pendant olefin arm; the products of experiments aiming at coordinating it to the Mo atom eluded isolation. I thus does not seem suitable for the synthesis of complexes with imido/olefin or imido/allyl ligands. However, products 1–3, (two of which (1, 3) were also characterised by single crystal X-ray diffraction) are nevertheless interesting, e.g., with respect to the grafting of molybdenum complexes
在 (丙烯)Mo(=O)(=NH) 和 (烯丙基)Mo(=O)(=NH) 表面物质作为 SOHIO 过程中间体的背景下,H2N–C6H4–CH2–CH=测试了 CH–CH3 (I),用于在高价 Mo 中心引入螯合亚胺/烯烃或亚胺/烯丙基配体。I 与 Na2[MoO4] 和三甲基氯硅烷反应生成 [Cl2Mo(=N–C6H4–CH2–CH=CH–CH3)2(dme)] (1),包含侧链烯烃臂。所有将烯烃引入 Mo 中心配位球的尝试都失败了。对 [Cl2Mo(=O)(=N–C6H4–CH2–CH=CH–CH3)(dme)] (2) 进行了相同的观察,通过 1 和 [(dme)Cl2Mo(=O )2]。三当量的 I 与 [CpMoCl4'] 反应生成 [CpCl2Mo(=N–C6H4–CH2–CH=CH–CH3)],(3),同样带有一个侧链烯烃臂;旨在将其与 Mo 原子配位的实验产物避免了分离。因此,I
Photosolvolysis of 2-Allylated Anilines to 2-Indanols
It is shown that 2-allylatedanilines (cf. Schemes 2–4, 7, and 8) on irradiation in protic solvents such as H2O. MeOH, and EtOH in the presence of H2SO4 undergo a novel photosolvolysis reaction to yield specifically trans-2-hydroxy- and trans-2-alkoxy-1-methylindanes. Intermediates are presumably tricyclo[4.3.0.01,8]nona-2,4-dienes formed in an intramolecular [2s + 2s] cycloaddition reaction (cf. Scheme
结果表明,在质子传递溶剂(如H 2 O. MeOH和EtOH)中,在H 2 SO 4存在下,辐照2-烯丙基化的苯胺(参见方案2-4、7和8)经历了新的光解反应特别地产生反式-2-羟基和反式-2-烷氧基-1-甲基茚满。中间体大概是在分子内[2 s + 2 s ]环加成反应中形成的三环[4.3.0.0 1,8 ] nona-2,4-二烯(参见方案7)。另一方面,N,N,N-三甲基-2-(1'-甲基烯丙基)苯胺盐18(方案6)和2-(3'-丁烯基)-N,N-二甲基苯胺(17)在MeOH或H 2 SO 4 / MeOH中辐射后,铵基还原生成(1-甲基烯丙基)苯(19)和1-甲基茚满(20)。
Ionic diamine rhodium complex catalyzed hydroaminomethylation of 2-allylanilines
作者:Kazumi Okuro、Howard Alper
DOI:10.1016/j.tetlet.2010.07.048
日期:2010.9
Ionic diamine rhodium complexes catalyze the hydroaminomethylation of 2-allylanilines. The reaction involves initial hydroformylation followed by reductive amination, which provides direct access to 1,2,3,4-tetrahydroquinolines and 2,3,4,5-1H-1-benzazepines. (C) 2010 Elsevier Ltd. All rights reserved.