tert-butyl (S)-1-(3-hydroxypropyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate | 1015076-99-9

• 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 (S)-1-(3-hydroxypropyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate
• 英文别名: tert-butyl (1S)-1-(3-hydroxypropyl)-6,7-dimethoxy-3,4-dihydro-1H-isoquinoline-2-carboxylate
• CAS: 1015076-99-9
• 化学式: C₁₉H₂₉NO₅
• 分子量: 351.443
• InChiKey: AGXFADIVFNQSFM-HNNXBMFYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  25
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.63
• 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 (S)-1-(3-hydroxypropyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate 在 4-二甲氨基吡啶 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 23.0h， 生成
  参考文献：
  名称：

  N-甲苯磺酰基-和N- Nosylaldimines的Rh催化对映选择性烯丙基化：（-）-Crispine A的全合成

  摘要：

  实现了N -Ts-和N -Ns-醛亚胺的不对称Rh催化的1,2-烯丙基化的空前发展。该方案利用烯丙基三氟硼酸钾和各种醛亚胺在3.0 mol％Rh（I）/ L1b催化剂存在下产生对映体富集的均烯丙基胺，产率高达90％，ee（R = H）和非对映选择性为10：1（ R = Me或Ph），使用（E）-和（Z）-巴豆基三氟硼酸钾时，会产生相同的主要非对映异构体。在（-）-crispine A的全合成中也说明了其合成效用。

  DOI：

  10.1021/acs.orglett.7b03523
• 作为产物：
  描述：

  在 甲醇 、 Candida antarctica lipase B 、 sucrose 、 Burkholderia cepacia lipase PS 、 水 、 potassium carbonate 作用下， 以 正己烷 、 甲基叔丁基醚 、 氯仿 为溶剂， 反应 178.0h， 生成 tert-butyl (S)-1-(3-hydroxypropyl)-6,7-dimethoxy-3,4-dihydroisoquinoline-2(1H)-carboxylate
  参考文献：
  名称：

  Total synthesis of crispine A enantiomers through a Burkholderia cepacia lipase-catalysed kinetic resolution

  摘要：

  Both enantiomers of the antitumour-active alkaloid crispine A (ee = 95%) were synthesised through the Burkholderia cepacia lipase-catalysed acylation of the primary hydroxy group of N-Boc-protected 1-(3-hydroxypropyl)-6,7-bis(methyloxy)-1,2,3,4-tetrahydroisoquinoline (+/-)-3 and the enantioselective hydrolysis of the corresponding O-decanoate (+/-)-4 [R = (CH2)(8)Me] with a remote, four-atom distant stereogenic centre. High enantioselectivities were observed for the (S)-selective O-acylation with vinyl decanoate in the presence of Et3N and Na2SO4 in t-BuOMe at 45 degrees C (E = 68), and for the (S)-selective hydrolysis with H2O in t-BuOMe at 45 degrees C (E = 52). The enzymatic resolutions, performed in two steps, afforded the key alcohol and ester enantiomers with high enantiomeric excesses (ee >= 94%). Ring-closure reactions of alcohol enantiomers (+)-3 and (-)-3 with thionyl chloride afforded the desired crispine A enantiomers (+)-1 and (-)-1 (ee >= 95%). (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.06.026

文献信息

• A convergent and stereoselective total synthesis of (−)-crispine A, (−)-benzo[a]quinolizidine and (−)-salsolidine
  作者：N. Siva Senkar Reddy、B. Jagan Mohan Reddy、B.V. Subba Reddy

  DOI：10.1016/j.tetlet.2013.05.132

  日期：2013.8

  A novel strategy has been developed for the syntheses of (−)-crispine, (−)-benzo[a]quinolizidine, and (−)-salsolidine using (R)-tert-butanesulfinamide as a source of chirality. The approach involves the stereoselective addition of Grignard reagent to chiral N-sulfinyl imine followed by cyclization of the secondary amide with a tethered halide as key steps.

  使用（R）-叔丁亚磺酰胺作为手性来源，已经开发了一种用于合成（-）-crispine，（-）-苯并[ a ]喹啉嗪和（-）-salsolidine的新策略。该方法涉及将格氏试剂立体选择性地加入手性N-亚磺酰基亚胺中，然后将关键酰胺与束缚的卤化物环化成第二酰胺。
• Synthesis of (-)-Trolline, (-)-Crispine A and (-)-Crispine E
  作者：Takashi Itoh、Takuya Kanemitsu、Yuki Yamashita、Kazuhiro Nagata

  DOI：10.3987/com-07-s(w)52

  日期：——
• Total synthesis of crispine A enantiomers through a Burkholderia cepacia lipase-catalysed kinetic resolution
  作者：Enikő Forró、László Schönstein、Ferenc Fülöp

  DOI：10.1016/j.tetasy.2011.06.026

  日期：2011.6

  Both enantiomers of the antitumour-active alkaloid crispine A (ee = 95%) were synthesised through the Burkholderia cepacia lipase-catalysed acylation of the primary hydroxy group of N-Boc-protected 1-(3-hydroxypropyl)-6,7-bis(methyloxy)-1,2,3,4-tetrahydroisoquinoline (+/-)-3 and the enantioselective hydrolysis of the corresponding O-decanoate (+/-)-4 [R = (CH2)(8)Me] with a remote, four-atom distant stereogenic centre. High enantioselectivities were observed for the (S)-selective O-acylation with vinyl decanoate in the presence of Et3N and Na2SO4 in t-BuOMe at 45 degrees C (E = 68), and for the (S)-selective hydrolysis with H2O in t-BuOMe at 45 degrees C (E = 52). The enzymatic resolutions, performed in two steps, afforded the key alcohol and ester enantiomers with high enantiomeric excesses (ee >= 94%). Ring-closure reactions of alcohol enantiomers (+)-3 and (-)-3 with thionyl chloride afforded the desired crispine A enantiomers (+)-1 and (-)-1 (ee >= 95%). (C) 2011 Elsevier Ltd. All rights reserved.
• Rh-Catalyzed Enantioselective Allylation of <i>N</i>-Tosyl- and <i>N</i>-Nosylaldimines: Total Synthesis of (−)-Crispine A
  作者：Pei-Fen Chiang、Wei-Sian Li、Jia-Hong Jian、Ting-Shen Kuo、Ping-Yu Wu、Hsyueh-Liang Wu

  DOI：10.1021/acs.orglett.7b03523

  日期：2018.1.5

  The unprecedented development of asymmetric Rh-catalyzed 1,2-allylation of N-Ts- and N-Ns-aldimines is achieved. This protocol utilizes potassium allyltrifluoroborates and various aldimines to generate enantioenriched homoallylic amines in the presence of 3.0 mol % of Rh(I)/L1b catalyst with up to 90% yield, 98% ee (R = H), and 10:1 diastereoselectivity (R = Me or Ph), yielding the same major diastereomer

  实现了N -Ts-和N -Ns-醛亚胺的不对称Rh催化的1,2-烯丙基化的空前发展。该方案利用烯丙基三氟硼酸钾和各种醛亚胺在3.0 mol％Rh（I）/ L1b催化剂存在下产生对映体富集的均烯丙基胺，产率高达90％，ee（R = H）和非对映选择性为10：1（ R = Me或Ph），使用（E）-和（Z）-巴豆基三氟硼酸钾时，会产生相同的主要非对映异构体。在（-）-crispine A的全合成中也说明了其合成效用。