(±)-tert-butyl 1-(hydroxymethyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate | 1024583-75-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 四氢异喹啉
• 英文名称: (±)-tert-butyl 1-(hydroxymethyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate
• 英文别名: tert-butyl 1-(hydroxymethyl)-6,7-dimethoxy-3,4-dihydro-1H-isoquinoline-2-carboxylate
• CAS: 1024583-75-2
• 化学式: C₁₇H₂₅NO₅
• 分子量: 323.389
• InChiKey: DWQKNWDRJQFXDA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  68.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (±)-tert-butyl 1-(hydroxymethyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate 在 盐酸 、 Candida antarctica lipase B 、 水 作用下， 以 正己烷 为溶剂， 60.0 ℃ 、8.0 MPa 条件下， 反应 5.0h， 生成 (R)-(6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolin-1-yl)methanol
  参考文献：
  名称：

  Continuous-flow enzymatic resolution strategy for the acylation of amino alcohols with a remote stereogenic centre: synthesis of calycotomine enantiomers

  摘要：

  Both enantiomers of calycotomine (R)-5 and (S)-5 were prepared through the CAL-B-catalysed asymmetric O-acylation of N-Boc-protected (6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolin-1-yl)methanol [(+/-)-3)]. The optimum conditions for the enzymatic resolution were determined under continuous-flow conditions, while the preparative-scale resolution of (+/-)-3 was performed as a batch reaction with high enantiselectivity (E>200). The resulting amino alcohol (S)-3 and amino ester (R)-4, obtained with high enantiomeric excess (ee = 99%), were transformed into the desired calycotomine (S)-5 and (R)-5 (ee = 99%). A systematic study was carried out in a continuous-flow system on the O-acylation of tetrahydroisoquinoline amino alcohol homologues (+/-)-1 to (+/-)-3 containing a remote stereogenic centre. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.01.006
• 作为产物：
  描述：

  叔-丁基氯甲酸酯 在 sodium tetrahydroborate 、 二异丁基氢化铝 、 三乙胺 、 2,3-二氯-5,6-二氰基-1,4-苯醌 作用下， 以 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 4.75h， 生成 (±)-tert-butyl 1-(hydroxymethyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate
  参考文献：
  名称：

  DDQ 促进 N-酰基/磺酰基 1,2,3,4-四氢异喹啉的温和高效无金属氧化 α-氰化

  摘要：

  N-酰基/磺酰基 1,2,3,4-四氢异喹啉 (THIQ) 的温和且高效的无金属氧化 α-氰化反应已在环境温度下通过 DDQ 氧化和随后的 N-酰基/磺酰基亚胺的捕获完成(n-Bu)3SnCN 离子。使用易于去除的 N-酰基/磺酰基作为保护基团而不是 N-芳基使天然产物合成中的应用范围广泛。使用 (±)-calycotomine 的短而有效的形式全合成分三个步骤说明了该方法的合成效用。

  DOI：

  10.3390/molecules23123223

文献信息

• Continuous-flow enzymatic resolution strategy for the acylation of amino alcohols with a remote stereogenic centre: synthesis of calycotomine enantiomers
  作者：László Schönstein、Enikő Forró、Ferenc Fülöp

  DOI：10.1016/j.tetasy.2013.01.006

  日期：2013.2

  Both enantiomers of calycotomine (R)-5 and (S)-5 were prepared through the CAL-B-catalysed asymmetric O-acylation of N-Boc-protected (6,7-dimethoxy-1,2,3,4-tetrahydroisoquinolin-1-yl)methanol [(+/-)-3)]. The optimum conditions for the enzymatic resolution were determined under continuous-flow conditions, while the preparative-scale resolution of (+/-)-3 was performed as a batch reaction with high enantiselectivity (E>200). The resulting amino alcohol (S)-3 and amino ester (R)-4, obtained with high enantiomeric excess (ee = 99%), were transformed into the desired calycotomine (S)-5 and (R)-5 (ee = 99%). A systematic study was carried out in a continuous-flow system on the O-acylation of tetrahydroisoquinoline amino alcohol homologues (+/-)-1 to (+/-)-3 containing a remote stereogenic centre. (C) 2013 Elsevier Ltd. All rights reserved.
• DDQ-Promoted Mild and Efficient Metal-Free Oxidative α-Cyanation of N-Acyl/Sulfonyl 1,2,3,4-Tetrahydroisoquinolines
  作者：Hong Kim、Heesun Yu、Hyoungsu Kim、Seok-Ho Kim、Dongjoo Lee

  DOI：10.3390/molecules23123223

  日期：——

  N-acyl/sulfonyl iminium ions with (n-Bu)3SnCN. Employing readily removable N-acyl/sulfonyl groups as protecting groups rather than N-aryl ones enables a wide range of applications in natural product synthesis. The synthetic utility of the method was illustrated using a short and efficient formal total synthesis of (±)-calycotomine in three steps.

  N-酰基/磺酰基 1,2,3,4-四氢异喹啉 (THIQ) 的温和且高效的无金属氧化 α-氰化反应已在环境温度下通过 DDQ 氧化和随后的 N-酰基/磺酰基亚胺的捕获完成(n-Bu)3SnCN 离子。使用易于去除的 N-酰基/磺酰基作为保护基团而不是 N-芳基使天然产物合成中的应用范围广泛。使用 (±)-calycotomine 的短而有效的形式全合成分三个步骤说明了该方法的合成效用。