<2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-<2-(tert-butyldimethylsiloxy)ethyl>-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy | 144467-91-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: <2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-<2-(tert-butyldimethylsiloxy)ethyl>-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy
• CAS: 144467-91-4
• 化学式: C₇₄H₁₂₈NO₁₃PSi₄
• 分子量: 1383.14
• InChiKey: LTZBEWKODSKLEB-GFFATAMOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  20.66
• 重原子数：
  93.0
• 可旋转键数：
  31.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.72
• 拓扑面积：
  151.62
• 氢给体数：
  0.0
• 氢受体数：
  14.0

反应信息

• 作为反应物：
  描述：

  <2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-<2-(tert-butyldimethylsiloxy)ethyl>-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy 在 氟化氢吡啶 作用下， 以 四氢呋喃 为溶剂， 反应 8.0h， 以76%的产率得到<2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-(2-hydroxyethyl)-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy-3,7,8,10,12-pentam
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024
• 作为产物：
  描述：

  <4S>-4-benzyl-3-(3,3,4-trimethyl-4-pentenoyl)-2-oxazolidinone 在 吡啶 、 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 双(乙腈)氯化钯(II) 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium periodate 、 Wilkinson's catalyst 、 四氧化锇 、 锂硼氢 、 9-borabicyclo[3.3.1]nonane dimer 、 草酰氯 、 偶氮二甲酸二叔丁酯 、 三氟化硼乙醚 、 氢氟酸 、 水 、 双氧水 、 三甲基铝 、 sodium hexamethyldisilazane 、 四氯化钛 、 sodium hydride 、 二异丁基氢化铝 、 戴斯-马丁氧化剂 、 溶剂黄146 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 2-(Phenylsulfonyl)-3-phenyloxaziridin 、 三乙胺 、 N,N-二异丙基乙胺 、 三苯基膦 、 2,3-二氯-5,6-二氰基-1,4-苯醌 、 magnesium bromide 、 tetramethylammonium triacetoxyborohydride 、 三氯化磷 、 儿萘酚硼烷 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 甲苯 、 乙腈 、 苯 为溶剂， 反应 253.08h， 生成 <2Z,4E,6E,8E,10S,11S,12R,13R,15R,15(2S,3S,5S,7R,8R,9S)>-15-<9-(tert-butyldimethylsiloxy)-7-<2-(tert-butyldimethylsiloxy)ethyl>-3--4,4,8-trimethyl-1,6-dioxaspiro<4.5>dec-2-yl>-11,13-bis(tert-butyldimethylsiloxy)-15-methoxy
  参考文献：
  名称：

  Total synthesis of (+)-calyculin A

  摘要：

  A convergent asymmetric synthesis of the marine natural product calyculin A has been accomplished through the union of the two subunits comprising the C1-C25 and C26-C37 portions of the molecule. These fragments were constructed utilizing auxiliary-based asymmetric aldol, alkylation, hydroxylation, and Michael reactions to establish 10 of the 15 stereogenic centers, The remaining chirality was incorporated through internal asymmetric induction. Stereoselective Wittig coupling of the two fragments and subsequent deprotection provided synthetic calyculin A. The spectral properties of the synthetic material were in complete agreement with those of the natural material except for the optical rotation which was equal and opposite in sign to that of the natural material. The absolute configuration of (-)-calyculin A has thus been shown to be opposite to that illustrated in structure 1.

  DOI：

  10.1021/ja00050a024