(3S,1'S,2'S)-1-tert-Butyldiphenylsiloxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-propoxy)hex-5-en | 214959-70-3

• 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: (3S,1'S,2'S)-1-tert-Butyldiphenylsiloxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-propoxy)hex-5-en
• 英文别名: N-[(1S,2S)-1-[(3S)-1-[tert-butyl(diphenyl)silyl]oxy-3-methylhex-5-en-3-yl]oxy-1-phenylpropan-2-yl]-2,2,2-trifluoroacetamide
• CAS: 214959-70-3
• 化学式: C₃₄H₄₂F₃NO₃Si
• 分子量: 597.793
• InChiKey: STRHFJXCKFAWSH-YHZHOBPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.11
• 重原子数：
  42
• 可旋转键数：
  14
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  (3S,1'S,2'S)-1-tert-Butyldiphenylsiloxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-propoxy)hex-5-en 在 臭氧 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 4.5h， 生成 (3R,5RS,1'S,2'S)-1-tert-Butyldiphenylsiloxy-3,7-dimethyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-propoxy)-5-octanol
  参考文献：
  名称：

  First Total Synthesis and Determination of the Absolute Configuration of the Stress Factor (+)-Hydroxymyoporone

  摘要：

  The first total synthesis of the stress factor (+)-hydroxymyoporone (4) is presented. The key step is an asymmetric allylation of the methyl ketone 10 which proceeds with excellent selectivity and yield. In addition, it was proven that the allylation assignment of the absolute configuration of hydroxymyoporone published in the natural literature is incorrect; the correct structure of the (+)-enantiomer is depicted in the structural formula 4.

  DOI：

  10.1002/(sici)1521-3765(19991001)5:10<2885::aid-chem2885>3.0.co;2-8
• 作为产物：
  描述：

  4-((tert-butyldiphenylsilyl)oxy)butan-2-one 、 (1S,2S)-N-(trifluoroacetyl)norpseudoephedrine trimethylsilyl ether 、 烯丙基三甲基硅烷 在 三氟甲磺酸 作用下， 以 二氯甲烷 为溶剂， 反应 17.0h， 生成 (3S,1'S,2'S)-1-tert-Butyldiphenylsiloxy-3-methyl-3-(1'-phenyl-2'-trifluoroacetamido-1'-propoxy)hex-5-en
  参考文献：
  名称：

  大环内酯类抗生素5,6-二氢cineromycin B的全合成。

  摘要：

  在大环内酯类抗生素5，6-四氢cineromycin B的第一个全合成中，三个构造单元会聚在一起。甲基酮的面部选择性烯丙基化是合成的关键步骤。TBDMS ＝叔丁基二甲基甲硅烷基，PMB ＝对甲氧基苄基。

  DOI：

  10.1002/1521-3773(20010302)40:5<901::aid-anie901>3.0.co;2-f

文献信息

• Synthesis of Enantiopure Homoallylic Alcohols
  作者：Lutz F. Tietze、Kai Schiemann、Christoph Wegner、Christian Wulff

  DOI：10.1002/(sici)1521-3765(19980904)4:9<1862::aid-chem1862>3.0.co;2-c

  日期：1998.9.4

  A highly selective asymmetric domino allylation of aliphatic ketones is described. When methyl ketones 1a-g, the chiral trimethylsilyl ether 2, and allylsilane 3 react in the presence of catalytic amounts of trifluoromethanesulfonic acid, the homoallylic ethers 4a-g are produced with up to 24:1 diastereoselectivity and 89% yield. Cleavage of the obtained tertiary homoallylic ethers C using lithium or sodium in liquid ammonia gives the homoallytic alcohols 5 in 75 to 95% yield and up to 92% ee. Even ethyl methyl ketone 1a, the most difficult example, showed a stereoselectivity of 9:1 at -78 degrees C and 24:1 at -109 degrees C. In addition, the allylation of protected hydroxyalkyl methyl ketones 7a-j was investigated to give the corresponding homoallylic ethers 8a-j with a diastereoselectivity of up to >24:1 and 98% yield. In contrast, ethyl alkyl ketones 1h-j have a low selectivity.
• Total Synthesis of the Macrolide Antibiotic 5,6-Dihydrocineromycin B
  作者：Lutz F. Tietze、Ludwig Völkel

  DOI：10.1002/1521-3773(20010302)40:5<901::aid-anie901>3.0.co;2-f

  日期：2001.3.2

  Three building blocks are coupled convergently in the first total synthesis of the macrolide antibiotic 5,6-tetrahydrocineromycin B (1); the facial selective allylation of a methyl ketone is the key step of the synthesis. TBDMS=tert-butyldimethylsilyl, PMB=p-methoxybenzyl.

  在大环内酯类抗生素5，6-四氢cineromycin B的第一个全合成中，三个构造单元会聚在一起。甲基酮的面部选择性烯丙基化是合成的关键步骤。TBDMS ＝叔丁基二甲基甲硅烷基，PMB ＝对甲氧基苄基。
• First Total Synthesis and Determination of the Absolute Configuration of the Stress Factor (+)-Hydroxymyoporone
  作者：Lutz F. Tietze、Christoph Wegner、Christian Wulff

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2885::aid-chem2885>3.0.co;2-8

  日期：1999.10.1

  The first total synthesis of the stress factor (+)-hydroxymyoporone (4) is presented. The key step is an asymmetric allylation of the methyl ketone 10 which proceeds with excellent selectivity and yield. In addition, it was proven that the allylation assignment of the absolute configuration of hydroxymyoporone published in the natural literature is incorrect; the correct structure of the (+)-enantiomer is depicted in the structural formula 4.