(E)-methyl benzyl(buta-1,3-dienyl)carbamate

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (E)-methyl benzyl(buta-1,3-dienyl)carbamate
• 英文别名: methyl N-benzyl-N-[(1E)-buta-1,3-dienyl]carbamate
• 化学式: C₁₃H₁₅NO₂
• 分子量: 217.268
• InChiKey: JSNPGZNXVRNQGM-ONNFQVAWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.15
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-methyl benzyl(buta-1,3-dienyl)carbamate 在 三氟化硼乙醚 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.17h， 生成 rac-(1S,6S)-methyl 7-(benzyl(methoxycarbonyl)amino)-1-hydroxyspiro[5.5]undec-8-ene-2-carboxylate
  参考文献：
  名称：

  The enantioselective synthesis of tetracyclic methyllycaconitine analogues

  摘要：

  A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels-Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.026
• 作为产物：
  描述：

  苄胺 在 magnesium sulfate 、 N,N-二异丙基乙胺 作用下， 以 乙醚 为溶剂， 反应 1.42h， 生成 (E)-methyl benzyl(buta-1,3-dienyl)carbamate
  参考文献：
  名称：

  The enantioselective synthesis of tetracyclic methyllycaconitine analogues

  摘要：

  A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels-Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.08.026

文献信息

• Design and Development of Highly Effective Lewis Acid Catalysts for Enantioselective Diels−Alder Reactions
  作者：Yong Huang、Tetsuo Iwama、Viresh H. Rawal

  DOI：10.1021/ja026088t

  日期：2002.5.1

  report describes the design and development of chiral Co(III)-salen catalysts for enantioselective Diels-Alder reactions. A crystal structure of a Co-salen catalyst with two equivalents of benzaldehyde provided insight on the factors that may be important for enantioselectivity. On the basis of this structural information, new catalysts were prepared in which the "bay region" tert-butyl groups were replaced

  本报告描述了用于对映选择性 Diels-Alder 反应的手性 Co(III)-salen 催化剂的设计和开发。具有两当量苯甲醛的 Co-salen 催化剂的晶体结构提供了对对映选择性可能很重要的因素的见解。在此结构信息的基础上，制备了新的催化剂，其中“湾区”叔丁基被三甲基甲硅烷基取代。新的甲硅烷基取代的催化剂非常有效（催化剂负载量低至 0.05 mol%），并且在室温、空气气氛下使用最少量的溶剂时使​​用方便。
• Carbon-Substituted Co(III) Salens as Effective Catalysts for Enantioselective Diels-Alder Reactions
  作者：Viresh H. Rawal、Jeff D. McGilvra

  DOI：10.1055/s-2004-834799

  日期：——

  place of the bay region t-Bu or silyl substituents were synthesized and examined as catalysts for the enantioselective Diels-Alder reaction of 1-benzylaminocarbamate-1,3-butadiene and methacrolein. The results were consistent with a working model for rationalizing enantioselectivity in these cycloaddition reactions: an increase in the steric bulk of the internal substituents gives, in most instances

  合成了七个新合成的 Co(III) salen 六氟锑酸盐配合物，其具有芳基或烷基-芳基取代基取代了湾区 t-Bu 或甲硅烷基取代基，并作为 1-苄氨基氨基甲酸酯-1,3 的对映选择性 Diels-Alder 反应的催化剂进行了研究-丁二烯和异丁烯醛。结果与在这些环加成反应中合理化对映选择性的工作模型一致：在大多数情况下，内部取代基空间体积的增加会导致加合物 ee 的可预测增加。最好的结果是用均苄基取代的 salen 获得的，与之前研究的 TMS-Co(III) salen 相比，它产生了 >97% ee 的环加合物，并且反应速率增加。这项研究的见解表明螺旋不对称，由增加内部取代基的空间尺寸引起的，单独不能解释产品的ee增加。本研究还表明，完全基于碳的取代基可以作为与三烷基硅烷一样有效的对映体区分元素，并且与硅烷不同，不易发生原脱甲硅烷化。
• Broadly Effective Enantioselective Diels−Alder Reactions of 1-Amino-substituted-1,3-butadienes
  作者：Yong Huang、Tetsuo Iwama、Viresh H. Rawal

  DOI：10.1021/ol0255716

  日期：2002.4.1

  [GRAPHICS]A broad range of substituted 1-amino-1,3-butadienes undergo enantloselective Diels-Alder reactions with methacrolein in the presence of 5 mol % of Cr(III)-salen complex 1. The reactions are carried out conveniently, at room temperature, and they afford the cycloadducts in high yields and excellent ee's.
• The enantioselective synthesis of tetracyclic methyllycaconitine analogues
  作者：Kevin Sparrow、David Barker、Margaret A. Brimble

  DOI：10.1016/j.tet.2011.08.026

  日期：2011.10

  A new enantioselective synthesis of ABEF ring analogues of methyllycaconitine has been developed using a chiral cobalt(III) salen-catalyzed Diels-Alder reaction to form the B ring. Subsequent elaboration to form the A, E and F rings was achieved by sequential Dieckmann, Mannich and Wacker-type cyclizations to afford tetracyclic analogues in 97.5% ee. (C) 2011 Elsevier Ltd. All rights reserved.