(1R,3S,4S,5R)-3-((S)-2-Benzyloxy-1-methyl-ethyl)-1,4-dimethyl-8-triisopropylsilanyloxymethyl-2,9-dioxa-bicyclo[3.3.1]non-7-en-6-one | 137628-54-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,3S,4S,5R)-3-((S)-2-Benzyloxy-1-methyl-ethyl)-1,4-dimethyl-8-triisopropylsilanyloxymethyl-2,9-dioxa-bicyclo[3.3.1]non-7-en-6-one
• CAS: 137628-54-7
• 化学式: C₂₉H₄₆O₅Si
• 分子量: 502.767
• InChiKey: MBMBFAIIODMXIW-QUBLTZHUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.68
• 重原子数：
  35.0
• 可旋转键数：
  11.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  53.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (1R,3S,4S,5R)-3-((S)-2-Benzyloxy-1-methyl-ethyl)-1,4-dimethyl-8-triisopropylsilanyloxymethyl-2,9-dioxa-bicyclo[3.3.1]non-7-en-6-one 在 sodium tetrahydroborate 、 cerium(III) chloride 、 di(tert-butyl)-biphenyl 、 lithium 、 间氯过氧苯甲酸 、 sodium phosphate 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 为溶剂， 反应 24.08h， 生成 (1R,2R,4R,5S,6S,7S,8S)-8-((S)-2-Hydroxy-1-methyl-ethyl)-1,7-dimethyl-2-triisopropylsilanyloxymethyl-3,9,10-trioxa-tricyclo[4.3.1.0^2,4]decan-5-ol
  参考文献：
  名称：

  A total synthesis of (.+-.)-tirandamycin B

  摘要：

  The total synthesis of the dienoyl tetramic acid antibiotic (+/-)-tirandamycin B is described. The key transformations of the strategy include (1) cyclization of pyranone 14 with fluorosilicic acid to provide the 2,6-dioxabicyclo[3.3.1]nonane system of the natural product, (2) reductive removal of the benzyl ether from enone 15, and (3) attachment of the tetramic acid moiety by using the Schlessinger phosphonate protocol. Protection of the primary hydroxyl function of tirandamycin B as the triisopropylsilyl (TIPS) ether was crucial to the success of the strategy.

  DOI：

  10.1021/ja00023a029
• 作为产物：
  描述：

  (R)-2-[(1R,2S,3S)-4-Benzyloxy-2-(tert-butyl-dimethyl-silanyloxy)-1,3-dimethyl-butyl]-6-hydroxy-6-methyl-5-triisopropylsilanyloxymethyl-6H-pyran-3-one 在 六氟合硅酸 、 氢氟酸 作用下， 以 乙腈 为溶剂， 反应 0.33h， 以35%的产率得到(1R,3S,4S,5R)-3-((S)-2-Benzyloxy-1-methyl-ethyl)-1,4-dimethyl-8-triisopropylsilanyloxymethyl-2,9-dioxa-bicyclo[3.3.1]non-7-en-6-one
  参考文献：
  名称：

  A total synthesis of (.+-.)-tirandamycin B

  摘要：

  The total synthesis of the dienoyl tetramic acid antibiotic (+/-)-tirandamycin B is described. The key transformations of the strategy include (1) cyclization of pyranone 14 with fluorosilicic acid to provide the 2,6-dioxabicyclo[3.3.1]nonane system of the natural product, (2) reductive removal of the benzyl ether from enone 15, and (3) attachment of the tetramic acid moiety by using the Schlessinger phosphonate protocol. Protection of the primary hydroxyl function of tirandamycin B as the triisopropylsilyl (TIPS) ether was crucial to the success of the strategy.

  DOI：

  10.1021/ja00023a029