(1S,3S)-3-Cyanomethyl-1-[2-(tert-butyldiphenylsilyloxy)ethyl]-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole | 179939-63-0

• 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: (1S,3S)-3-Cyanomethyl-1-[2-(tert-butyldiphenylsilyloxy)ethyl]-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole
• 英文别名: 2-[(1S,3S)-1-[2-[tert-butyl(diphenyl)silyl]oxyethyl]-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indol-3-yl]acetonitrile
• CAS: 179939-63-0
• 化学式: C₃₁H₃₅N₃OSi
• 分子量: 493.724
• InChiKey: YFLKREAKTBNNHG-BTYSJIOQSA-N

物化性质

• 沸点：
  635.0±55.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  36
• 可旋转键数：
  8
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.32
• 拓扑面积：
  60.8
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,3S)-3-Cyanomethyl-1-[2-(tert-butyldiphenylsilyloxy)ethyl]-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole 在 palladium on activated charcoal 盐酸 、 草酰氯 、 potassium tert-butylate 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.5h， 生成 suaveoline
  参考文献：
  名称：

  A total asymmetric synthesis of (–)-suaveoline

  摘要：

  A new total synthesis of (-)-suaveoline from L-tryptophan is reported (overall yield ca. 14%); key steps include a high yielding cis-specific Pictet-Spengler reaction, a one-pot Horner-Wadsworth-Emmons/alkylation procedure, a vinylogous Thorpe cyclization and the direct formation of a pyridine from a 1,5-dinitrile.

  DOI：

  10.1039/cc9960001479
• 作为产物：
  描述：

  3-(tert-butyldiphenylsilyloxy)-1-propanal 在 3 A molecular sieve 、 三氟乙酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 (1S,3S)-3-Cyanomethyl-1-[2-(tert-butyldiphenylsilyloxy)ethyl]-2,3,4,9-tetrahydro-1H-pyrido[3,4-b]indole
  参考文献：
  名称：

  A total asymmetric synthesis of (–)-suaveoline

  摘要：

  A new total synthesis of (-)-suaveoline from L-tryptophan is reported (overall yield ca. 14%); key steps include a high yielding cis-specific Pictet-Spengler reaction, a one-pot Horner-Wadsworth-Emmons/alkylation procedure, a vinylogous Thorpe cyclization and the direct formation of a pyridine from a 1,5-dinitrile.

  DOI：

  10.1039/cc9960001479

文献信息

• Stereoselectivity and conformational control in the synthesis of ajmaline and epi-ajmaline alkaloids
  作者：Patrick D. Bailey、Mark A. Beard、Mark Cresswell、Hoa P.T. Dang、Ravindra B. Pathak、Theresa R. Phillips、Richard A. Price

  DOI：10.1016/j.tetlet.2013.01.074

  日期：2013.3

  Careful choice of the N-protecting group provides crucial conformational control, allowing ring-closure to the indole 3-position in the late stages of the synthesis of ajmaline alkaloids; the choice of protecting group and reducing agent can also provide access to either the natural or epi configuration at the indole 2-position.

  仔细选择N-保护基团可提供关键的构象控制，从而在阿玛琳生物碱合成的后期使环闭合至吲哚3-位。保护基和还原剂的选择还可以提供在吲哚2-位的天然或epi构型的途径。
• Thecis-Specific Pictet−Spengler Reaction
  作者：Laura Alberch、Patrick D. Bailey、Paul D. Clingan、Timothy J. Mills、Richard A. Price、Robin G. Pritchard

  DOI：10.1002/ejoc.200400017

  日期：2004.5

  The Pictet-Spengler reaction of tryptophan allyl ester with aryl aldehydes generates cis-tetrahydro-b-carbolines with complete stereo-control and with complete retention of optical integrity, when the reaction is carried out under kinetically controlled conditions. [on SciFinder (R)]

  当反应在动力学控制的条件下进行时，色氨酸烯丙基酯与芳基醛的 Pictet-Spengler 反应生成具有完全立体控制和完全保留光学完整性的顺式四氢-b-咔啉。[在 SciFinder (R) 上]
• The total synthesis of (−)-suaveoline
  作者：Patrick D. Bailey、Keith M. Morgan

  DOI：10.1039/b005695m

  日期：——

  A new synthesis of the indole alkaloid (−)-suaveoline from L-tryptophan is reported (overall yield ca. 14%). Key synthetic steps include a high yielding cis-specific Pictet–Spengler reaction, a one-pot Horner–Wadsworth–Emmons and alkylation procedure, a vinylogous Thorpe cyclisation and the direct formation of a 3,4,5-trisubstituted pyridine from a 1,5-dinitrile. The direct conversion of ajmaline to

  的新综合 吲哚生物碱 （-）-suaveoline来自 L-色氨酸据报道（总收率约为14％）。关键的合成步骤包括高产量的顺式Pictet-Spengler反应，一锅Horner-Wadsworth-Emmons和烷基化 程序，乙烯基索普 环化 并直接形成3,4,5-三取代 吡啶从1，5-二苯胺。直接转换阿玛琳 还描述了半合成的suaveoline。
• Unexpected cis selectivity in the Pictet–Spengler reaction
  作者：Patrick D. Bailey、Mark A. Beard、Theresa R. Phillips

  DOI：10.1016/j.tetlet.2009.03.121

  日期：2009.7

  Whilst cis:trans selectivity of about 4:1 can be obtained from Pictet-Spengler reactions between tryptophan methyl esters and aldehydes using conditions of kinetic control, much higher cis selectivity (>95:5) can be obtained when both the tryptophan derivative and the aldehyde possess a Suitable pi-system: preliminary results oil the scope and limitations of this exceptional stereocontrol are presented in this Letter. (C) 2009 Elsevier Ltd. All rights reserved.
• A total asymmetric synthesis of (–)-suaveoline
  作者：Patrick D. Bailey、Keith M. Morgan

  DOI：10.1039/cc9960001479

  日期：——

  A new total synthesis of (-)-suaveoline from L-tryptophan is reported (overall yield ca. 14%); key steps include a high yielding cis-specific Pictet-Spengler reaction, a one-pot Horner-Wadsworth-Emmons/alkylation procedure, a vinylogous Thorpe cyclization and the direct formation of a pyridine from a 1,5-dinitrile.