(S)-1-allyl-1,2-dihydro-2-(2,2,2-trichloroethoxycarbonyl)-β-carboline | 316789-86-3

• 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-1,2-dihydro-2-(2,2,2-trichloroethoxycarbonyl)-β-carboline
• 英文别名: 2,2,2-trichloroethyl (1S)-1-prop-2-enyl-1,9-dihydropyrido[3,4-b]indole-2-carboxylate
• CAS: 316789-86-3
• 化学式: C₁₇H₁₅Cl₃N₂O₂
• 分子量: 385.677
• InChiKey: UJZPVVSAYOKVGO-AWEZNQCLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.9
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.24
• 拓扑面积：
  45.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (S)-1-allyl-1,2-dihydro-2-(2,2,2-trichloroethoxycarbonyl)-β-carboline 在 三乙基硅烷 、 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 0.75h， 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
• 作为产物：
  描述：

  9-[N-[p-(tert-Amyl)phenylsulfonyl]-L-prolinyl]-β-carboline 在 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 24.5h， 生成 (S)-1-allyl-1,2-dihydro-2-(2,2,2-trichloroethoxycarbonyl)-β-carboline
  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

• A New Entry to Asymmetric Synthesis of 1-Substituted 1,2,3,4-Tetrahydro-β-carbolines Employing a Pyroglutamic Acid Derivative as a Chiral Auxiliary
  作者：Takashi Itoh、Kazuhiro Nagata、Masashi Yokoya、Michiko Miyazaki、Sachiko Ikeda、Yuji Matsuya、Yasuko Enomoto、Akio Ohsawa

  DOI：10.1055/s-2002-31931

  日期：——

  β-Carboline which was protected at N-9 by an acyl group derived from L-pyroglutamic acid reacted with allyltributyltin or silyl enol ethers in the presence of an alkyl chloroformate in a highly diastereoselective manner to give 1-substituted 1,2-dihydro-β-carbolines. The compounds were readily transformed to the corresponding asymmetric 1-substituted tetrahydro-β-carbolines that are common partial

  在 N-9 位被 L-焦谷氨酸衍生的酰基保护的 β-咔啉在氯甲酸烷基酯存在下以高度非对映选择性的方式与烯丙基三丁基锡或甲硅烷基烯醇醚反应，得到 1-取代的 1,2-二氢- β-咔啉。这些化合物很容易转化为相应的不对称 1-取代四氢-β-咔啉，这是各种吲哚生物碱中常见的部分结构。
• A general method for the asymmetric synthesis of both enantiomers of 1-substituted 1,2,3,4-tetrahydro-β-carbolines employing pyroglutamic acid derivatives as chiral auxiliaries
  作者：Takashi Itoh、Michiko Miyazaki、Sachiko Ikeda、Kazuhiro Nagata、Masashi Yokoya、Yuji Matsuya、Yasuko Enomoto、Akio Ohsawa

  DOI：10.1016/s0040-4020(03)00420-4

  日期：2003.5

  9-(S)-Pyroglutaminyl-beta-carbolines were allowed to react with a nucleophile (allyltributyltin or a silyl enol ether) in the presence of 2,2,2-trichloroethyl chloroformate to give 1,2-addition products in good yields and high diastereoselectivity. The chiral auxiliary at N-9 was readily removed by a mild hydrolysis. The same chiral source afforded both enantiomers by simply altering a protecting group of the amide nitrogen. That is, (S)-pyroglutaminyl groups which had an N-alkyl group afforded the (S) isomer, whereas the ones having an N-acyl group produced the (R) isomer of the addition products. (C) 2003 Elsevier Science Ltd. All rights reserved.
• A Selective Synthesis of Both Enantiomers of a 1-Allyl-b-carboline Using the Same Chiral Auxiliary Derived from L-Proline
  作者：Akio Ohsawa、Yûji Matsuya、Takashi Itoh、Yasuko Enomoto

  DOI：10.3987/com-00-9050

  日期：——
• 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.