tert-butyl ((4R,6E)-4-{[tert-butyl(dimethyl)silyl]oxy}-8-oxooct-6-en-1-yl)carbamate | 1274953-66-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: tert-butyl ((4R,6E)-4-{[tert-butyl(dimethyl)silyl]oxy}-8-oxooct-6-en-1-yl)carbamate
• 英文别名: (R,E)-tert-butyl 4-(tert-butyldimethylsilyloxy)-8-oxooct-6-enylcarbamate；tert-butyl N-[(E,4R)-4-[tert-butyl(dimethyl)silyl]oxy-8-oxooct-6-enyl]carbamate
• CAS: 1274953-66-0
• 化学式: C₁₉H₃₇NO₄Si
• 分子量: 371.593
• InChiKey: URQUYTIKIDUEGJ-SCOAYWHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.83
• 重原子数：
  25
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.79
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  tert-butyl ((4R,6E)-4-{[tert-butyl(dimethyl)silyl]oxy}-8-oxooct-6-en-1-yl)carbamate 在 咪唑 、 (S)-(-)-5,5-二氯-6,6-二甲氧基-2,2-双(二苯基磷酸)-1,1-联苯基 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 Hoveyda-Grubbs catalyst second generation 、 caesium carbonate 、 4-氯-3-硝基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 45.0h， 生成 (R)-4-((4S,6S)-6-((2S,3E,6S,7E,10R)-13-((tert-butoxycarbonyl)amino)-6,10-bis((tert-butyldimethylsilyl)oxy)-2-hydroxytrideca-3,7-dien-1-yl)-2,2-dimethyl-1,3-dioxan-4-yl)-3-hydroxybutyl pivalate
  参考文献：
  名称：

  C(21)−C(40) of Tetrafibricin via Metal Catalysis: Beyond Stoichiometric Chiral Reagents, Auxiliaries, and Premetalated Nucleophiles

  摘要：

  The C(21)-C(40) fragment of fibrinogen receptor inhibitor tetrafibricin was prepared in 12 steps from propane diol (longest linear sequence). In this approach, 6 C-C bonds are formed via asymmetric iridium catalyzed transfer hydrogenative carbonyl allylation and 2 C=C bonds are formed via Grubbs olefin cross-metathesis.

  DOI：

  10.1021/ol200735r
• 作为产物：
  描述：

  4-(N-叔丁氧羰基氨基)-1-丁醇 在 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 N-甲基咪唑 、 bis(1,5-cyclooctadiene)diiridium(I) dichloride 、 caesium carbonate 、 R-(+)-1,1'-联萘-2,2'-双二苯膦 、 4-氯-3-硝基苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 48.0h， 生成 tert-butyl ((4R,6E)-4-{[tert-butyl(dimethyl)silyl]oxy}-8-oxooct-6-en-1-yl)carbamate
  参考文献：
  名称：

  C(21)−C(40) of Tetrafibricin via Metal Catalysis: Beyond Stoichiometric Chiral Reagents, Auxiliaries, and Premetalated Nucleophiles

  摘要：

  The C(21)-C(40) fragment of fibrinogen receptor inhibitor tetrafibricin was prepared in 12 steps from propane diol (longest linear sequence). In this approach, 6 C-C bonds are formed via asymmetric iridium catalyzed transfer hydrogenative carbonyl allylation and 2 C=C bonds are formed via Grubbs olefin cross-metathesis.

  DOI：

  10.1021/ol200735r

文献信息

• Enantio- and Diastereoselective Synthesis of (<i>E</i>)-1,5-<i>syn</i>-Diols: Application to the Synthesis of the C(23)−C(40) Fragment of Tetrafibricin
  作者：Jeremy Kister、Philippe Nuhant、Ricardo Lira、Achim Sorg、William R. Roush

  DOI：10.1021/ol2003836

  日期：2011.4.1

  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.
• 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
  作者：Philippe Nuhant、Jeremy Kister、Ricardo Lira、Achim Sorg、William R. Roush

  DOI：10.1016/j.tet.2011.06.008

  日期：2011.9

  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.
• C(21)−C(40) of Tetrafibricin <i>via</i> Metal Catalysis: Beyond Stoichiometric Chiral Reagents, Auxiliaries, and Premetalated Nucleophiles
  作者：Esa T. T. Kumpulainen、Byungsoo Kang、Michael J. Krische

  DOI：10.1021/ol200735r

  日期：2011.5.6

  The C(21)-C(40) fragment of fibrinogen receptor inhibitor tetrafibricin was prepared in 12 steps from propane diol (longest linear sequence). In this approach, 6 C-C bonds are formed via asymmetric iridium catalyzed transfer hydrogenative carbonyl allylation and 2 C=C bonds are formed via Grubbs olefin cross-metathesis.