(3S,5S)-2-[(E)-but-2-enyl]-5-[2-(1,3-dioxolan-2-yl)ethyl]-3-(1,3-dithian-2-yl)-6-trimethylsilylcyclohexan-1-one | 202646-33-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二噻烷
• 英文名称: (3S,5S)-2-[(E)-but-2-enyl]-5-[2-(1,3-dioxolan-2-yl)ethyl]-3-(1,3-dithian-2-yl)-6-trimethylsilylcyclohexan-1-one
• CAS: 202646-33-1
• 化学式: C₂₂H₃₈O₃S₂Si
• 分子量: 442.759
• InChiKey: CKCLLIGUYDXAPO-DAWNGBCWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.83
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  86.1
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,5S)-2-[(E)-but-2-enyl]-5-[2-(1,3-dioxolan-2-yl)ethyl]-3-(1,3-dithian-2-yl)-6-trimethylsilylcyclohexan-1-one 在 Raney Ni (W₄) 盐酸 、 氢气 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醇 、 苯 为溶剂， 反应 37.0h， 生成 (5R,6S,7aS)-5-butyl-6-methyl-1,2,5,6,7,7a-hexahydroinden-4-one
  参考文献：
  名称：

  Chiral [η6-Arene-Cr(CO)3] Complexes as Synthetic Building Blocks: A Short Enantioselective Total Synthesis of (+)-Ptilocaulin

  摘要：

  An enantioselective total synthesis of the marine natural product (+)-ptilocaulin is described. The synthesis starts from [anisole-Cr(CO)(3)], which is converted to [2-trimethylsilylanisole - Cr(Co)(3)] (greater than or equal to 99 % ee) by enantioselective deprotonation/silyLation and recrystallization. After attachment of a 2-butenyl side-chain, nucleophile addition (2-lithio-1,3-dithiane) followed by treatment with chloratrimethylsilane and hydrolysis leads to (5S,6S)-6-((E)-but-2-enyl)-5-[1,3]-dithian-2-yl-2-trimethylsilylcyclohex-2-enone with complete chirality transfer. This compound, which was characterized by X-ray crystallography, is transformed into (5 xi,6S,7aS)-5-butpl-6-methyl-1,2,5,6,7,7a-hexahydro-inden-4-one, a ptilocaulin precursor known from the literature, by a 4-step sequence consisting of diastereoselective 1,4-addition, ultrasound-assisted desulfurization/hydrogenation (Raney Ni) and aldol cyclization. The target molecule was prepared in both racemic and optically active form. The X-ray crystal structure of rac-ptilocaulin nitrate shows flat ribbons of homochiral units (parallel double chains) connected by an interesting pattern of hydrogen bonds between the guanidinium and the nitrate ions. A different mode of hydrogen bonding resulting in the formation of helical monochains was found in the solid-state structure of (+)-ptilocaulin co-crystallized with about 29 % of its C-3a epimer.

  DOI：

  10.1002/(sici)1521-3765(199801)4:1<57::aid-chem57>3.0.co;2-h
• 作为产物：
  描述：

  2-(2-溴乙基)-1,3-二恶烷 、 (5S,6S)-6-[(E)-but-2-enyl]-5-(1,3-dithian-2-yl)-2-trimethylsilylcyclohex-2-en-1-one 在 碘 、 magnesium 作用下， 生成 (3S,5S)-2-[(E)-but-2-enyl]-5-[2-(1,3-dioxolan-2-yl)ethyl]-3-(1,3-dithian-2-yl)-6-trimethylsilylcyclohexan-1-one
  参考文献：
  名称：

  Chiral [η6-Arene-Cr(CO)3] Complexes as Synthetic Building Blocks: A Short Enantioselective Total Synthesis of (+)-Ptilocaulin

  摘要：

  An enantioselective total synthesis of the marine natural product (+)-ptilocaulin is described. The synthesis starts from [anisole-Cr(CO)(3)], which is converted to [2-trimethylsilylanisole - Cr(Co)(3)] (greater than or equal to 99 % ee) by enantioselective deprotonation/silyLation and recrystallization. After attachment of a 2-butenyl side-chain, nucleophile addition (2-lithio-1,3-dithiane) followed by treatment with chloratrimethylsilane and hydrolysis leads to (5S,6S)-6-((E)-but-2-enyl)-5-[1,3]-dithian-2-yl-2-trimethylsilylcyclohex-2-enone with complete chirality transfer. This compound, which was characterized by X-ray crystallography, is transformed into (5 xi,6S,7aS)-5-butpl-6-methyl-1,2,5,6,7,7a-hexahydro-inden-4-one, a ptilocaulin precursor known from the literature, by a 4-step sequence consisting of diastereoselective 1,4-addition, ultrasound-assisted desulfurization/hydrogenation (Raney Ni) and aldol cyclization. The target molecule was prepared in both racemic and optically active form. The X-ray crystal structure of rac-ptilocaulin nitrate shows flat ribbons of homochiral units (parallel double chains) connected by an interesting pattern of hydrogen bonds between the guanidinium and the nitrate ions. A different mode of hydrogen bonding resulting in the formation of helical monochains was found in the solid-state structure of (+)-ptilocaulin co-crystallized with about 29 % of its C-3a epimer.

  DOI：

  10.1002/(sici)1521-3765(199801)4:1<57::aid-chem57>3.0.co;2-h

文献信息

• Chiral [η6-Arene-Cr(CO)3] Complexes as Synthetic Building Blocks: A Short Enantioselective Total Synthesis of (+)-Ptilocaulin
  作者：Kurt Schellhaas、Hans-Günther Schmalz、Jan W. Bats

  DOI：10.1002/(sici)1521-3765(199801)4:1<57::aid-chem57>3.0.co;2-h

  日期：1998.1

  An enantioselective total synthesis of the marine natural product (+)-ptilocaulin is described. The synthesis starts from [anisole-Cr(CO)(3)], which is converted to [2-trimethylsilylanisole - Cr(Co)(3)] (greater than or equal to 99 % ee) by enantioselective deprotonation/silyLation and recrystallization. After attachment of a 2-butenyl side-chain, nucleophile addition (2-lithio-1,3-dithiane) followed by treatment with chloratrimethylsilane and hydrolysis leads to (5S,6S)-6-((E)-but-2-enyl)-5-[1,3]-dithian-2-yl-2-trimethylsilylcyclohex-2-enone with complete chirality transfer. This compound, which was characterized by X-ray crystallography, is transformed into (5 xi,6S,7aS)-5-butpl-6-methyl-1,2,5,6,7,7a-hexahydro-inden-4-one, a ptilocaulin precursor known from the literature, by a 4-step sequence consisting of diastereoselective 1,4-addition, ultrasound-assisted desulfurization/hydrogenation (Raney Ni) and aldol cyclization. The target molecule was prepared in both racemic and optically active form. The X-ray crystal structure of rac-ptilocaulin nitrate shows flat ribbons of homochiral units (parallel double chains) connected by an interesting pattern of hydrogen bonds between the guanidinium and the nitrate ions. A different mode of hydrogen bonding resulting in the formation of helical monochains was found in the solid-state structure of (+)-ptilocaulin co-crystallized with about 29 % of its C-3a epimer.