tert-butyl {(4R,6E,8R,10E,12R,14S,16S)-4,14,16-tris{[tert-butyl(dimethyl)silyl]oxy}-8,12-dihydroxy-18-[(4-methoxybenzyl)-oxy]octadeca-6,10-dien-1-yl}carbamate | 1274953-69-3

• 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: tert-butyl {(4R,6E,8R,10E,12R,14S,16S)-4,14,16-tris{[tert-butyl(dimethyl)silyl]oxy}-8,12-dihydroxy-18-[(4-methoxybenzyl)-oxy]octadeca-6,10-dien-1-yl}carbamate
• 英文别名: tert-butyl N-[(4R,6E,8R,10E,12R,14S,16S)-4,14,16-tris[[tert-butyl(dimethyl)silyl]oxy]-8,12-dihydroxy-18-[(4-methoxyphenyl)methoxy]octadeca-6,10-dienyl]carbamate
• CAS: 1274953-69-3
• 化学式: C₄₉H₉₃NO₉Si₃
• 分子量: 924.535
• InChiKey: UTRYRHTWRPQCGQ-DSKUUAOWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  12.47
• 重原子数：
  62
• 可旋转键数：
  31
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  125
• 氢给体数：
  3
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  tert-butyl {(4R,6E,8R,10E,12R,14S,16S)-4,14,16-tris{[tert-butyl(dimethyl)silyl]oxy}-8,12-dihydroxy-18-[(4-methoxybenzyl)-oxy]octadeca-6,10-dien-1-yl}carbamate 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 以90%的产率得到5.10.5. tert-butyl {(4R,6E,8R,10E,12R,14R,16S)-4,8,12,14,16-pentakis{[tert-butyl(dimethyl)silyl]oxy}-18-[(4-methoxybenzyl)oxy]octadeca-6,10-dien-1-yl}carbamate
  参考文献：
  名称：

  Development of a double allylboration reagent targeting 1,5-syn-(E)-diols: application to the synthesis of the C(23)–C(40) fragment of tetrafibricin

  摘要：

  Interest in the synthesis of the C(23) C(40) fragment 2 of tetrafibricin prompted us to develop a new method for the synthesis of 1,5-syn-(E)-diols. Toward this end, the kinetically controlled hydroboration of allenes 6, 33, ent-39, 42, and 45 with the Soderquist borane 25R were studied. Tetrabutylammonium allenyltrifluoroborate 45 gave superior results and was utilized in a double allylboration sequence with two different aldehydes to provide the targeted 1,5-syn-(E)-diols in generally high yields (72-98%), and with high enantioselectivity (>95% ee), diastereoselectivity (dr >20:1), and (E)/(Z) selectivity (>20:1). This new method was applied to the synthesis of the C(23) C(40) fragment 2 of tetrafibricin. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2011.06.008
• 作为产物：
  描述：

  (E)-5-(4-methoxy-benzyloxy)-pent-2-en-1-al 在 咪唑 、 2,6-二甲基吡啶 、 titanium(IV) isopropylate 、 sodium periodate 、 potassium dihydrogenphosphate 、 四氧化锇 、 (-)-diethyl tartrate 、 三氟化硼乙醚 、 红铝 、 sodium hydroxide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 甲醇 、 乙醚 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 叔丁醇 为溶剂， 反应 65.92h， 生成 tert-butyl {(4R,6E,8R,10E,12R,14S,16S)-4,14,16-tris{[tert-butyl(dimethyl)silyl]oxy}-8,12-dihydroxy-18-[(4-methoxybenzyl)-oxy]octadeca-6,10-dien-1-yl}carbamate
  参考文献：
  名称：

  Enantio- and Diastereoselective Synthesis of (E)-1,5-syn-Diols: Application to the Synthesis of the C(23)−C(40) Fragment of Tetrafibricin

  摘要：

  A highly stereoselective synthesis of (E)-1,5-syn-diols 6 Is described. The kinetically controlled hydroboration of allenyltrifluoroborate 8 with Soderquist borane 2 provides the (Z)-allylic trifluoroborate 9, which undergoes sequential allylboration with two different aldehydes to provide (E)-1,5-syn-diols 6 In 72-98% yields with > 95% ee and > 20:1 dr. Application of this method to the synthesis of the tetraflbricin C(23)-C(40) fragment 19 is described.

  DOI：

  10.1021/ol2003836

文献信息

• Development of a double allylboration reagent targeting 1,5-syn-(E)-diols: application to the synthesis of the C(23)–C(40) fragment of tetrafibricin [Tetrahedron 67 (35) (2011) 6497–6512]
  作者：Philippe Nuhant、Jeremy Kister、Ricardo Lira、Achim Sorg、William R. Roush

  DOI：10.1016/j.tet.2011.10.077

  日期：2012.1