4-benzyl-2-vinyl-1,4-benzoxazine | 176164-99-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并恶嗪类
• 英文名称: 4-benzyl-2-vinyl-1,4-benzoxazine
• 英文别名: (2R)-2-Ethenyl-3,4-dihydro-4-(phenylmethyl)-2H-1,4-benzoxazine；(2R)-4-benzyl-2-ethenyl-2,3-dihydro-1,4-benzoxazine
• CAS: 176164-99-1
• 化学式: C₁₇H₁₇NO
• 分子量: 251.328
• InChiKey: NUCVCEHAICYBTI-OAHLLOKOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  12.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-benzyl-2-vinyl-1,4-benzoxazine 在 palladium on activated charcoal 氢气 作用下， 以 乙醇 为溶剂， 生成 (R)-2-Ethyl-3,4-dihydro-2H-benzo[1,4]oxazine
  参考文献：
  名称：

  Asymmetric cyclization of 3,4-dihydro-2-vinyl-2H-1,4-benzoxazine catalyzed by palladium-BHMP catalyst

  摘要：

  The reaction of 1,4-diacetoxy-cis-2-butene 20 with 2-(benzylamino)phenol 3 in THF in the presence of Et(3)N and a catalytic amount of Pd(0)-BHMP-beta-Ala Ic gave optically active 4-benzyl-2-vinylbenzoxazine of up to 56.2%ee. The reaction of (Z)-2-butene-1,4-diylbis(methylcarbonate) 2b instead of 20 with 2-(benzylamino)phenol 3, 4 was obtained with e.e. up to 71.4%. We could improve the enantioselectivity of (R)-4 by introducing a carboxyl group at the terminal position of the pendant side chain on the bisphosphine ligand and by using a methyl carbonate ester 2b instead of diacetate 2a.

  DOI：

  10.1016/0957-4166(96)00018-3
• 作为产物：
  描述：

  carbonic acid (Z)-4-methoxycarbonyloxy-but-2-enyl ester methyl ester 、 o-(benzylamino)phenol 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 BHMP-β-Ala 作用下， 以 四氢呋喃 为溶剂， 反应 37.0h， 生成 4-benzyl-2-vinyl-1,4-benzoxazine 、 4-benzyl-2-vinyl-1,4-benzoxazine
  参考文献：
  名称：

  Asymmetric cyclization of 3,4-dihydro-2-vinyl-2H-1,4-benzoxazine catalyzed by palladium-BHMP catalyst

  摘要：

  The reaction of 1,4-diacetoxy-cis-2-butene 20 with 2-(benzylamino)phenol 3 in THF in the presence of Et(3)N and a catalytic amount of Pd(0)-BHMP-beta-Ala Ic gave optically active 4-benzyl-2-vinylbenzoxazine of up to 56.2%ee. The reaction of (Z)-2-butene-1,4-diylbis(methylcarbonate) 2b instead of 20 with 2-(benzylamino)phenol 3, 4 was obtained with e.e. up to 71.4%. We could improve the enantioselectivity of (R)-4 by introducing a carboxyl group at the terminal position of the pendant side chain on the bisphosphine ligand and by using a methyl carbonate ester 2b instead of diacetate 2a.

  DOI：

  10.1016/0957-4166(96)00018-3

文献信息

• Palladium-catalyzed asymmetric tandem allylic substitution using chiral 2-(phosphinophenyl)pyridine ligand
  作者：Katsuji Ito、Yoshikatsu Imahayashi、Tomomi Kuroda、Shuuichiro Eno、Bunnai Saito、Tsutomu Katsuki

  DOI：10.1016/j.tetlet.2004.08.014

  日期：2004.9

  Palladium-catalyzed asymmetric tandem allylic substitution of (Z)-1,4-diacyloxy- and (Z)-1,4-bis(alkoxycarbonyloxy)-2-utene (2a-c) using 2-(phosphinophenyl)pyridine 1 as chiral ligand provided optically active six-membered 2-vinyl-1,4-diheterocyclic compounds with good to high enantioselectivity. For example, the reactions with catechol, 2-(benzylamino) phenol, or 1,2-bis(benzylamino)ethane as a nucleophile gave 2-vinyl-1,4-benzodioxane (71% ee), 4-benzyl-2-vinyl-1,4-benzoxazine (86% ee), and 1,4-dibenzyl-2-vinylpiperazine (86% ee), respectively. (C) 2004 Elsevier Ltd. All rights reserved.
• Asymmetric cyclization of 3,4-dihydro-2-vinyl-2H-1,4-benzoxazine catalyzed by palladium-BHMP catalyst
  作者：Akira Yamazaki、Issei Achiwa、Kazuo Achiwa

  DOI：10.1016/0957-4166(96)00018-3

  日期：1996.2

  The reaction of 1,4-diacetoxy-cis-2-butene 20 with 2-(benzylamino)phenol 3 in THF in the presence of Et(3)N and a catalytic amount of Pd(0)-BHMP-beta-Ala Ic gave optically active 4-benzyl-2-vinylbenzoxazine of up to 56.2%ee. The reaction of (Z)-2-butene-1,4-diylbis(methylcarbonate) 2b instead of 20 with 2-(benzylamino)phenol 3, 4 was obtained with e.e. up to 71.4%. We could improve the enantioselectivity of (R)-4 by introducing a carboxyl group at the terminal position of the pendant side chain on the bisphosphine ligand and by using a methyl carbonate ester 2b instead of diacetate 2a.