(4R,4aS,6R,10S,12S,12aR)-4-(tert-Butyldimethylsiloxy)-1,2,4,4a,5,6,10,11,12,12a-decahydro-6,8-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-7(1H)-one | 150931-03-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 萘并呋喃类
• 英文名称: (4R,4aS,6R,10S,12S,12aR)-4-(tert-Butyldimethylsiloxy)-1,2,4,4a,5,6,10,11,12,12a-decahydro-6,8-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-7(1H)-one
• CAS: 150931-03-6
• 化学式: C₂₆H₄₆O₆Si
• 分子量: 482.733
• InChiKey: MLADZCVSXWCRIU-MLJUQEBCSA-N

反应信息

• 作为反应物：
  描述：

  (4R,4aS,6R,10S,12S,12aR)-4-(tert-Butyldimethylsiloxy)-1,2,4,4a,5,6,10,11,12,12a-decahydro-6,8-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-7(1H)-one 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 反应 1.0h， 以97%的产率得到(4R,4aS,6R,7S,12S,12aR)-4-(tert-Butyldimethylsiloxy)dodecahydro-6,7-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-8(2H)-one
  参考文献：
  名称：

  A-Ring oxygenation studies in bridgehead hydroxyl-substituted trans-tricyclo[9.3.1.03,8]pentadecan-14-one congeners of taxol

  摘要：

  The ready availability of 5 has prompted examination of a convenient means for carbonyl transposition in its A-ring. Attempts to implement such chemistry directly on 5 and its silyl-protected derivative suffer from a kinetic proclivity for transannular capture of the enolate anion. This undesirable process was circumvented by reduction of the C9 carbonyl following conversion to silyl enol ether 8. Once the resulting 9alpha-alcohol was protected as its MOM ether, the enolates of 10a and 10b could be efficiently oxygenated at C13 by treatment with the Davis sulfonyl oxaziridine despite severe steric congestion in that locale. The resultant alpha-alcohol 11a could be epimerized to the 13beta-isomer by exposure to potassium hexamethyldisilazide. Remarkably, 11a is prone to autoxidation, although the yield of diketone 12 is capricious. A preferred route to this key intermediate involves periodinane oxidation of 11a. Reduction of 12 and its O-silylated derivative has provided the targeted compounds 15 and 16, respectively. The conformational features of various intermediates are discussed in the light of NMR studies and MM2 calculations.

  DOI：

  10.1021/jo00070a037
• 作为产物：
  描述：

  (4R,4aS,6R,8R,10R,12S,12aR)-4-(tert-Butyldimethylsiloxy)dodecahydro-6,8-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-7(1H)-one 在 戴斯-马丁氧化剂 作用下， 以 二氯甲烷 为溶剂， 反应 0.17h， 以85%的产率得到(4R,4aS,6R,10S,12S,12aR)-4-(tert-Butyldimethylsiloxy)-1,2,4,4a,5,6,10,11,12,12a-decahydro-6,8-dihydroxy-12-(methoxymethoxy)-12a,13,13-trimethyl-6,10-methanobenzocyclodecen-7(1H)-one
  参考文献：
  名称：

  A-Ring oxygenation studies in bridgehead hydroxyl-substituted trans-tricyclo[9.3.1.03,8]pentadecan-14-one congeners of taxol

  摘要：

  The ready availability of 5 has prompted examination of a convenient means for carbonyl transposition in its A-ring. Attempts to implement such chemistry directly on 5 and its silyl-protected derivative suffer from a kinetic proclivity for transannular capture of the enolate anion. This undesirable process was circumvented by reduction of the C9 carbonyl following conversion to silyl enol ether 8. Once the resulting 9alpha-alcohol was protected as its MOM ether, the enolates of 10a and 10b could be efficiently oxygenated at C13 by treatment with the Davis sulfonyl oxaziridine despite severe steric congestion in that locale. The resultant alpha-alcohol 11a could be epimerized to the 13beta-isomer by exposure to potassium hexamethyldisilazide. Remarkably, 11a is prone to autoxidation, although the yield of diketone 12 is capricious. A preferred route to this key intermediate involves periodinane oxidation of 11a. Reduction of 12 and its O-silylated derivative has provided the targeted compounds 15 and 16, respectively. The conformational features of various intermediates are discussed in the light of NMR studies and MM2 calculations.

  DOI：

  10.1021/jo00070a037