S-(2-Pyridyl) (1S,3aR,4S,5R,7aS)-1-ethyl-5-<2-(trimethylsilyl)ethynyl>-2,3,3a,4,5,7a-hexahydro-1H-indene-4-carboxythiolate | 153868-82-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: S-(2-Pyridyl) (1S,3aR,4S,5R,7aS)-1-ethyl-5-<2-(trimethylsilyl)ethynyl>-2,3,3a,4,5,7a-hexahydro-1H-indene-4-carboxythiolate
• 英文别名: S-pyridin-2-yl (1S,3aR,4S,5R,7aS)-1-ethyl-5-(2-trimethylsilylethynyl)-2,3,3a,4,5,7a-hexahydro-1H-indene-4-carbothioate
• CAS: 153868-82-7
• 化学式: C₂₂H₂₉NOSSi
• 分子量: 383.63
• InChiKey: NYDQXOCWXHFMMI-WXRGLTTHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  26
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.55
• 拓扑面积：
  55.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  S-(2-Pyridyl) (1S,3aR,4S,5R,7aS)-1-ethyl-5-<2-(trimethylsilyl)ethynyl>-2,3,3a,4,5,7a-hexahydro-1H-indene-4-carboxythiolate 在 四丁基氟化铵 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 3.83h， 生成 (1S,3aR,4S,5R,7aS)-1-Ethyl-5-ethynyl-4-(2-pyrrolylcarbonyl)-2,3,3a,4,5,7a-hexahydro-1H-indene
  参考文献：
  名称：

  Total synthesis of ionophore antibiotic X-14547 A (indanomycin)

  摘要：

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.

  DOI：

  10.1021/jo00081a010
• 作为产物：
  描述：

  tert-Butyl <(1S,2R,3S)-3-ethyl-2-<(E)-5-(trimethylsilyl)-2-penten-4-ynoyl>cyclopent-1-yl>acetate 在 4-二甲氨基吡啶 、 sodium hydroxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 达卡巴嗪 、 三乙胺 、 三苯基膦 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 甲苯 为溶剂， 反应 71.42h， 生成 S-(2-Pyridyl) (1S,3aR,4S,5R,7aS)-1-ethyl-5-<2-(trimethylsilyl)ethynyl>-2,3,3a,4,5,7a-hexahydro-1H-indene-4-carboxythiolate
  参考文献：
  名称：

  Total synthesis of ionophore antibiotic X-14547 A (indanomycin)

  摘要：

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.

  DOI：

  10.1021/jo00081a010

文献信息

• Total synthesis of ionophore antibiotic X-14547 A (indanomycin)
  作者：Steven D. Burke、Anthony D. Piscopio、Michael E. Kort、Mark A. Matulenko、Marshall H. Parker、David M. Armistead、K. Shankaran

  DOI：10.1021/jo00081a010

  日期：1994.1

  A convergent, enantioselective total synthesis of ionophore antibiotic X-14547A (indanomycin, 1) is described. The dioxanone-to-dihydropyran variant of the lactonic Ireland-Claisen rearrangement establishes the hydropyran nucleus of the ''left wing'' fragment 2. Elaboration to the target synthon utilizes a new methodology for the preparation of stereodefined vinylsilanes (24 --> 25 --> 26) via net S(N)2' coupling of [alpha-(mesyloxy)allyl]silanes with Grignard reagents catalyzed by CuCN. Salient features in the construction of the ''right wing'' subunit 3 include a modification of the Noyori three-component coupling procedure (32 --> 33) and the application,of a retro hetero Diels-Alder/intramolecular Diels-Alder (''mock Claisen'') process (5 --> 39), Palladium-mediated cross Coupling of ''left wing'' and ''right wing'' synthons using Stille's method tolerates a free carboxylic acid and an unprotected acyl pyrrole, affording indanomycin directly in its natural absolute configuration.