(S)-1-allyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole | 181218-86-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物 - 哈马拉生物碱
• 英文名称: (S)-1-allyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole
• 英文别名: (S)-1-allyl-1,2,3,4-tetrahydro-β-carboline；1-allyl-1,2,3,4-tetrahydro-β-carboline；(1S)-1-prop-2-enyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole
• CAS: 181218-86-0
• 化学式: C₁₄H₁₆N₂
• 分子量: 212.294
• InChiKey: WLFXPRUMDXLARV-ZDUSSCGKSA-N

物化性质

• 沸点：
  383.6±32.0 °C(Predicted)
• 密度：
  1.094±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.29
• 拓扑面积：
  27.8
• 氢给体数：
  2
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (S)-1-allyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole 在 Grubbs catalyst first generation sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 三乙胺 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 10.5h， 生成 indoloquinolizidine
  参考文献：
  名称：

  以手性 1-Allyl-1,2,3,4-tetrahydro-b-carboline 作为合成 1,2,3,4,6,7,12,12b-Octahydroindolo[2,3-a]quinolizine 和 Harmicine起始材料

  摘要：

  (S)-1,2,3,4,6,7,12,12b-octahydroindolo[2,3-a]quinolizine 和 (S)-harmicine 的全合成使用手性 1-allyl-1,2 ,3,4-四氢-β-咔啉作为原料。

  DOI：

  10.3987/com-03-9968
• 作为产物：
  描述：

  9-[N-[p-(tert-Amyl)phenylsulfonyl]-L-prolinyl]-β-carboline 在 三乙基硅烷 、 sodium hydroxide 、 溶剂黄146 、 三氟乙酸 、 锌 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 25.25h， 生成 (S)-1-allyl-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole
  参考文献：
  名称：

  Preparation of both enantiomers of 1-allyl-1,2,3,4-tetrahydro-β-carboline using allyltin reagents and a chiral auxiliary derived from l-proline

  摘要：

  beta -Carboline, which had an acyl group derived from L-proline at the 9-position, reacted with allyltributyltin and 2,2,2-trichloroethyl chloroformate, to afford an 1-allyl-1,2-dihydro-beta -carboline derivative in a diastereo selective manner. The chiral acyl group at N-9 was readily eliminated by aqueous alkali to give a corresponding carboxylic acid. The formed 1-allyl-1,2-dihydro-beta -carboline was transformed via two reduction steps to 1-alkyl-1,2,3,4-tetrahydro-beta -carboline in high ee. When the allylation was carried out using tetraallyltin instead of allyltributyltin, the stereoselectivity was reversed, and the antipode of the allyl adduct was obtained in high yield and ee in the presence of tin(IV) tetraiodide. Thus, it was found that both enantiomers of 1-allyl-beta -carboline were obtained in good enantioselectivities by the use of the same chiral auxiliary. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(01)00684-6

文献信息

• Asymmetric Allylboration of Cyclic Imines and Applications to Alkaloid Synthesis
  作者：T. Robert Wu、J. Michael Chong

  DOI：10.1021/ja0636791

  日期：2006.8.1

  Treatment of cyclic imines with 3,3'-disubstituted binaphthol modified allylboronates provides the expected allylated products in good yields and with high stereoselectivities (91-99% ee). The products may be readily transformed into various alkaloids.

  用 3,3'-二取代联萘酚改性的烯丙基硼酸酯处理环状亚胺以良好的产率和高立体选择性 (91-99% ee) 提供预期的烯丙基化产物。产物可以很容易地转化为各种生物碱。
• Proline-Catalyzed Asymmetric Addition Reaction of 9-Tosyl-3,4-dihydro-β-carboline with Ketones
  作者：Takashi Itoh、Masashi Yokoya、Keiko Miyauchi、Kazuhiro Nagata、Akio Ohsawa

  DOI：10.1021/ol030103x

  日期：2003.11.1

  [reaction: see text] 9-Tosyl-3,4-dihydro-beta-carboline (1) reacted with a ketone in the presence of (S)-proline as a catalyst to give the corresponding addition product in good yield and high enantioselectivity. In the process, a small amount of water was found to affect the stereoselectivity of the products. The system was applied to reaction of compound 1 and 3-buten-2-one to give 3,4,6,7,12,12

  [反应：见正文]在（S）-脯氨酸作为催化剂的存在下，9-Tosyl-3,4-dihydro-beta-carboline（1）与酮反应，以高收率和高对映选择性得到相应的加成产物。在此过程中，发现少量水会影响产品的立体选择性。将该体系用于化合物1和3-丁烯-2-酮的反应，得到3,4,6,7,12,12b-六氢-1H-吲哚并[2,3-a]喹诺嗪-2-酮，是合成某些吲哚生物碱的通用前体。
• One-Pot Chemoenzymatic Cascade for the Enantioselective C(1)-Allylation of Tetrahydroisoquinolines
  作者：Jack J. Sangster、Rebecca E. Ruscoe、Sebastian C. Cosgrove、Juan Mangas-Sánchez、Nicholas J. Turner

  DOI：10.1021/jacs.2c09176

  日期：2023.3.1

  enantioenriched C(1)-allylated tetrahydroisoquinolines. This transformation couples a monoamine oxidase (MAO-N)-catalyzed oxidation with a metal catalyzed allylboration, followed by a biocatalytic deracemization to afford allylic amine derivatives in both high yields and good to high enantiomeric excess. The cascade is operationally simple, with all components added at the start of the reaction and can

  在此，我们报告了用于合成富含对映体的 C(1)-烯丙基化四氢异喹啉的一锅化学酶促过程。这种转化将单胺氧化酶 (MAO-N) 催化的氧化与金属催化的烯丙基硼化偶联，然后进行生物催化去外消旋化，以高产率和良好到高对映体过量提供烯丙基胺衍生物。级联操作简单，所有组分都在反应开始时添加，可用于生成关键构建块以供进一步阐述。
• Enantioselective Allylzincation of Cyclic Aldimines in the Presence of Anionic Bis-oxazoline Ligand
  作者：Masaharu Nakamura、Atsushi Hirai、Eiichi Nakamura

  DOI：10.1021/ja961213k

  日期：1996.1.1
• Preparation of both enantiomers of 1-allyl-1,2,3,4-tetrahydro-β-carboline using allyltin reagents and a chiral auxiliary derived from l-proline
  作者：Takashi Itoh、Yûji Matsuya、Yasuko Enomoto、Akio Ohsawa

  DOI：10.1016/s0040-4020(01)00684-6

  日期：2001.8

  beta -Carboline, which had an acyl group derived from L-proline at the 9-position, reacted with allyltributyltin and 2,2,2-trichloroethyl chloroformate, to afford an 1-allyl-1,2-dihydro-beta -carboline derivative in a diastereo selective manner. The chiral acyl group at N-9 was readily eliminated by aqueous alkali to give a corresponding carboxylic acid. The formed 1-allyl-1,2-dihydro-beta -carboline was transformed via two reduction steps to 1-alkyl-1,2,3,4-tetrahydro-beta -carboline in high ee. When the allylation was carried out using tetraallyltin instead of allyltributyltin, the stereoselectivity was reversed, and the antipode of the allyl adduct was obtained in high yield and ee in the presence of tin(IV) tetraiodide. Thus, it was found that both enantiomers of 1-allyl-beta -carboline were obtained in good enantioselectivities by the use of the same chiral auxiliary. (C) 2001 Elsevier Science Ltd. All rights reserved.