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indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one | 144633-21-6

中文名称
——
中文别名
——
英文名称
indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one
英文别名
20-Thia-10,17-diazapentacyclo[11.7.0.01,17.02,10.04,9]icosa-2,4,6,8-tetraen-18-one
indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-one化学式
CAS
144633-21-6
化学式
C17H18N2OS
mdl
——
分子量
298.409
InChiKey
ZWNSCHSPROLHKB-UHFFFAOYSA-N
BEILSTEIN
——
EINECS
——
  • 物化性质
  • 计算性质
  • ADMET
  • 安全信息
  • SDS
  • 制备方法与用途
  • 上下游信息
  • 反应信息
  • 文献信息
  • 表征谱图
  • 同类化合物
  • 相关功能分类
  • 相关结构分类

计算性质

  • 辛醇/水分配系数(LogP):
    2.6
  • 重原子数:
    21
  • 可旋转键数:
    0
  • 环数:
    5.0
  • sp3杂化的碳原子比例:
    0.47
  • 拓扑面积:
    50.5
  • 氢给体数:
    0
  • 氢受体数:
    2

上下游信息

  • 下游产品
    中文名称 英文名称 CAS号 化学式 分子量

反应信息

  • 作为反应物:
    描述:
    indolo[1,2-a]octahydro-1-thia-3a-azacyclopenta[d]naphthylen-3-onesodium periodate乙酸酐对甲苯磺酸 作用下, 以 1,4-二氧六环甲醇甲苯 为溶剂, 反应 25.0h, 生成 10,17-diaza-20-thiahexacyclo[11.7.01,17.02,10.03,19.04,9]icosa-2(3),4(9),5,7-tetraen-18-one
    参考文献:
    名称:
    A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems
    摘要:
    A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.
    DOI:
    10.1021/jo991742h
  • 作为产物:
    参考文献:
    名称:
    Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles
    摘要:
    一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下,用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现,这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时,最初形成的N-酰基亚胺离子会快速失去质子,产生S,N-酮烯醇缩醛,比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果,这是分子内反应的立体化学产物的成因。分子力学计算表明,内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反,高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。
    DOI:
    10.1055/s-1994-25621
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文献信息

  • Cycloaddition Chemistry of Anhydro-4-hydroxy-1,3-thiazolium Hydroxides (Thioisomünchnones) for the Synthesis of Heterocycles
    作者:Albert Padwa、Scott R. Harring、Donald L. Hertzog、William R. Nadler
    DOI:10.1055/s-1994-25621
    日期:——
    A series of α,α-disubstituted thioisomünchnones were prepared by treating acyclic or cyclic thioamides with bromoacetyl chloride in the presence of triethylamine. The resulting mesoionic dipole was found to undergo bimolecular 1,3-dipolar cycloaddition with several different dipolarophiles. When a hydrogen atom is present in the α-position of the thioamide, the initially formed N-acyl iminium ion undergoes proton loss to produce a S,N-ketene acetal at a faster rate than thioisomünchnone formation. The cycloaddition behavior of several substituted thioisomünchnones which possess a tethered alkene were also examined. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring π-bond across the transient thioisomünchnone dipole. Molecular mechanics calculations reveal that the endo diastereomers are significantly lower in energy than the corresponding exo isomers. Attempts to cycloadd the thioisomünchnone dipole across a tethered indolyl ring were unsuccessful. Instead, products derived by nucleophilic cyclization of the indolyl ring onto the thio N-acyl iminium ion were formed in good yield.
    一系列的α,α-二取代硫代异肟酮通过在三乙胺存在下,用溴乙酰氯处理非环状或环状硫代酰胺来制备。结果发现,这些介离子偶极体会发生双分子1,3-偶极环加成反应与多种不同的偶极体分子。当硫代酰胺的α-位上有氢原子时,最初形成的N-酰基亚胺离子会快速失去质子,产生S,N-酮烯醇缩醛,比形成硫代异肟酮的速度更快。还研究了几种带有附加烯烃的取代硫代异肟酮的环加成行为。内向环加成反应是邻近的π键跨过瞬态硫代异肟酮偶极子的结果,这是分子内反应的立体化学产物的成因。分子力学计算表明,内向非对映异构体的能量比相应的向外构体显著更低。尝试将硫代异肟酮偶极子环加成到附加的吲哚环上未能成功。相反,高产率地形成通过吲哚环以亲核方式环化到硫代N-酰基亚胺离子上的产物。
  • π-Cyclization reactions of thio N-acyliminium ions for heterocyclic synthesis
    作者:Scott M. Sheehan、L. Scott Beall、Albert Padwa
    DOI:10.1016/s0040-4039(98)00902-2
    日期:1998.7
    Thio N-acyliminium ions are readily generated from the reaction of thioamides with bromoacetyl chloride. In the presence of tethered pi-nucleophiles, cyclization occurs to give S,N-acetals which can be further converted into various alkaloid skeletons. (C) 1998 Elsevier Science Ltd. All rights reserved.
  • A One-Pot Bicycloannulation Method for the Synthesis of Tetrahydroisoquinoline Systems
    作者:Albert Padwa、L. Scott Beall、Todd M. Heidelbaugh、Bing Liu、Scott M. Sheehan
    DOI:10.1021/jo991742h
    日期:2000.5.1
    A highly effective method for the synthesis of the core indolo[2,3-a]quinolizidine skeleton found in yohimbine is described. The reaction of N-monosubstituted thioamides with bromoalkenoyl chlorides furnishes thioisomunchnones as transient 1,3-dipoles that undergo ready intramolecular cycloaddition across the tethered pi-bond to give thio-bicycloannulated products in a one-pot operation. The stereochemical outcome of the intramolecular reaction is the consequence of an endo cycloaddition of the neighboring-bond across the transient thioisomunchnone dipole. A major limitation of the method is that when a hydrogen is present in the alpha-position of the thioamide the initially formed thio-N-acyliminium ion undergoes proton loss to produce a S ,N-ketene acetal at a faster rate than dipole formation. Treatment of tetrahydro-beta-carboline-1-thione with 2-bromooct-7-enoyl chloride followed by reductive removal of sulfur from the cycloadduct resulted in the formation of (+/-)-alloyahimbanone. Attempts to cycloadd the thioisomunchnone dipole across several nucleophilic-bonds failed, and instead, products derived from cyclization of the pi-bond onto the initially formed thio-N-acyliminium ion were formed. The resulting N,S-ketals were further converted into several tetrahydroisoquinoline alkaloids in good yield.
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