(RS)-meso-N-[2-(4,5-dihydro-3H-dinaphtho[2,1c:1',2'-e]azepinoethyl)]-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepine | 259796-48-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯氮卓类
• 英文名称: (RS)-meso-N-[2-(4,5-dihydro-3H-dinaphtho[2,1c:1',2'-e]azepinoethyl)]-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepine
• 英文别名: 13-[2-(13-azapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-yl)ethyl]-13-azapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaene
• CAS: 259796-48-0
• 化学式: C₄₆H₃₆N₂
• 分子量: 616.805
• InChiKey: QNHDAXGGOIYGTO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  10.7
• 重原子数：
  48
• 可旋转键数：
  3
• 环数：
  10.0
• sp3杂化的碳原子比例：
  0.13
• 拓扑面积：
  6.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  六氟磷酸银 、 (RS)-meso-N-[2-(4,5-dihydro-3H-dinaphtho[2,1c:1',2'-e]azepinoethyl)]-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepine 、 bis(μ-chloro)bis[(1,2,3-η)-cyclohexenyl]dipalladium 以 二氯甲烷 为溶剂， 以71%的产率得到[1-[(R)-4,5-dihydro-3H-dinaphtho[1,2-c:2',1'-e]azepino]-2-[(S)-4,5-dihydro-3H-dinaphtho[1,2-c:2',1'-e]azepino]ethane](η3-cyclohexenyl)palladium hexafluorophosphate
  参考文献：
  名称：

  Self-Adaptable Catalysts:  Substrate-Dependent Ligand Configuration

  摘要：

  Pd(II) allyl and Pd(0) olefin complexes containing the configurationally labile ligand 1,2-bis-[4,5dihydro-3H-dibenzo[c-e]azepino]ethane were studied as models for intermediates in Pd-catalyzed allylic alkylations. According to NMR and DFT studies, the ligand prefers C-s conformation in both eta(3)-1,3-diphenylpropenyl and eta(3)-cyclohexenyl Pd(II) complexes, whereas in Pd(0) olefin complexes it adopts different conformations in complexes derived from the two types of allyl systems in both solution and, as verified by X-ray crystallography, in the solid state. These results demonstrate that the Pd complex is capable of adapting its structure to the reacting substrate. The different structural preferences also provide an explanation for the behavior of 1,3-diphenyl-2-propenyl acetate and 2-cyclohexenyl acetate in Pd-catalyzed allylic alkylations using pseudo-C-2 and pseudo-C-s symmetric ligands.

  DOI：

  10.1021/ja074044k
• 作为产物：
  描述：

  (S)-2,2'-双(溴甲基)-1,1'-联萘 在 三乙胺 作用下， 以 甲苯 为溶剂， 反应 48.0h， 生成 (RS)-meso-N-[2-(4,5-dihydro-3H-dinaphtho[2,1c:1',2'-e]azepinoethyl)]-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepine
  参考文献：
  名称：

  Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium-Catalyzed Allylic Substitutions

  摘要：

  Chiral P,N-ligands with pseudo-C-2 and pseudo-C-s symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C-2-symmetric ligands based on the binaphthyl skeleton than with the analogous C-2-symmetric P,P- and N,N-analogues. Pseudo-C-2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.

  DOI：

  10.1021/jo026889e
• 作为试剂：
  描述：

  1,3-二溴-2-(2,6-二溴苯基)苯 在 sodium tetrahydroborate 、 (RS)-meso-N-[2-(4,5-dihydro-3H-dinaphtho[2,1c:1',2'-e]azepinoethyl)]-4,5-dihydro-3H-dinaphtho[2,1-c:1',2'-e]azepine 、 仲丁基锂 作用下， 以 甲醇 、 正己烷 、 环己烷 、 甲苯 为溶剂， 反应 0.25h， 生成 (RS)-6,6'-dibromobiphenyl-2,2'-dimethanol
  参考文献：
  名称：

  Asymmetric bromine–lithium exchange: on the importance of both the diamine ligand and the organolithium reagent

  摘要：

  对一系列具有手性前体的联苯进行了不对称溴-锂交换的研究。

  DOI：

  10.1039/c5cc06548h

文献信息

• Asymmetric Aziridination of Chalcone Promoted by Binaphthalene-Based Chiral Amines
  作者：Philip Page、Céline Bordogna、Ian Strutt、Yohan Chan、Benjamin Buckley

  DOI：10.1055/s-0033-1339643

  日期：——

  binaphthalene-based tertiary amines have been used for the asymmetric aziridination of chalcone, providing N-unprotected aziridines with ee values of up to 43%. A chiral hydrazinium salt has been isolated for the first time and shown to provide similar yield and enantioselectivity to the in situ process in reaction with chalcone.

  原位衍生自许多对映异构纯的联萘叔胺的胺已用于查耳酮的不对称氮丙啶化，提供 N-未保护的氮丙啶，其 ee 值高达 43%。首次分离出手性肼盐，并显示出与原位与查耳酮反应过程相似的产率和对映选择性。
• Chiral catalysis of additions of alkyllithiums to aldehydes
  作者：Jean Paul Mazaleyrat、Donald J. Cram

  DOI：10.1021/ja00405a052

  日期：1981.7
• Synthesis and resolution of axially chiral C2-symmetric 1,1′-binaphthyl-substituted tetramethylethylenediamines
  作者：Jean-Paul Mazaleyrat

  DOI：10.1016/s0957-4166(97)00301-7

  日期：1997.8

  The axially chiral TMEDA derivatives 1 and 2 in which tetramethylethylene-diamine is substituted respectively by one and two 1,1'-binaphthyl units at their 2,2'positions, are of interest as chiral catalysts. Experimental details of their preparation in enantiomerically pure form are given. Two different routes have been followed, involving alkylation of both N,N-dimethyl ethylenediamine and ethylenediamine by 2,2'bis-(bromomethyl)-1,1'-binaphthyl either enantiomerically pure as prepared from resolved 1,1'-binaphthyl-2,2'-dicarboxylic acid or racemic, the resulting racemic diamines 1 and 2 being then resolved with dibenzoyl-tartaric acid. (C) 1997 Elsevier Science Ltd.
• Shi, Min; Itoh, Nobuhiro; Masaki, Yukio, Journal of Chemical Research, Miniprint, 1996, # 8, p. 1946 - 1955
  作者：Shi, Min、Itoh, Nobuhiro、Masaki, Yukio

  DOI：——

  日期：——
• Influence of Steric Symmetry and Electronic Dissymmetry on the Enantioselectivity in Palladium-Catalyzed Allylic Substitutions
  作者：Jean-Luc Vasse、Robert Stranne、Raivis Zalubovskis、Carole Gayet、Christina Moberg

  DOI：10.1021/jo026889e

  日期：2003.4.1

  Chiral P,N-ligands with pseudo-C-2 and pseudo-C-s symmetry based on chiral pyrrolidine and phospholane rings or on dinaphthatodihydroazepino and dinaphthatodihydrophosphepino moieties were prepared and assessed in the palladium-catalyzed allylic substitutions of allylic acetates. Higher selectivity was achieved with pseudo-C-2-symmetric ligands based on the binaphthyl skeleton than with the analogous C-2-symmetric P,P- and N,N-analogues. Pseudo-C-2-type ligands had properties superior to those of pseudo-meso-type ligands when 1,3-diphenyl-2-propenyl acetate was used as a substrate, whereas the reverse situation was found for 3-cyclohexenyl acetate. Chirally flexible ligands, prepared by substitution of one of the rigid binaphthyl skeletons for a flexible biphenyl system, were found to induce chirality to the same extent as a 1:1 mixture of the rigid ligands.