trans-4,4,4-trifluoro-3-methyl-1-pehnyl-3-trimethylsilyloxy-1-butene

• 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: trans-4,4,4-trifluoro-3-methyl-1-pehnyl-3-trimethylsilyloxy-1-butene
• 英文别名: (E)-trimethyl((1,1,1-trifluoro-2-methyl-4-phenylbut-3-en-2-yl)oxy)silane；trimethyl-[(E)-1,1,1-trifluoro-2-methyl-4-phenylbut-3-en-2-yl]oxysilane
• 化学式: C₁₄H₁₉F₃OSi
• 分子量: 288.385
• InChiKey: VEUOAXKTSHEORM-ZHACJKMWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.87
• 重原子数：
  19
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  trans-4,4,4-trifluoro-3-methyl-1-pehnyl-3-trimethylsilyloxy-1-butene 在 盐酸 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以98%的产率得到2-hydroxy-2-methyl-4-phenyl-1,1,1-trifluorobut-3-ene
  参考文献：
  名称：

  CsF-Catalyzed Nucleophilic Trifluoromethylation of trans-Enones with Trimethyl(trifluoromethyl)silane:  A Facile Synthesis of trans-α-Trifluoromethyl Allylic Alcohols

  摘要：

  [GRAPHICS]Reactions of trans-enones, R-C=C-COR' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Pt, CFB) (la-e), with TMS-CF3 in the presence of catalytic amounts of cesium fluoride (CsF) in ethylene glycol dimethyl ether led to the formation of the corresponding trans-alpha-trifluoromethyl silyl ethers, R-C=C-C(OSiMe3)(CF3)R' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Pt, CFB) (2a-e), in essentially quantitative yield. On hydrolysis with aqueous HCl, the corresponding trans-alpha-trifluaromethyl allylic alcohols, R-C=C-C(OH)(CF3)R' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Et, CF3) (3a-e), were formed in >90% isolated yield. Under similar reaction conditions, 2-cyclohexen-1-one (1f) also gave trifluoromethyl allylic alcohols (3f) in 92% yield. The intermediates (2a-f) and products (3a-f) are liquids and were characterized by IR, H-1, (19)f and C-13 NMR, MS, and high-resolution mass spectroscopy (HRMS).

  DOI：

  10.1021/ol990844r
• 作为产物：
  描述：

  (三氟甲基)三甲基硅烷 、 苄叉丙酮 在 tris(2,4,6-trimethoxyphenyl)-phosphine 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 0.5h， 以92%的产率得到trans-4,4,4-trifluoro-3-methyl-1-pehnyl-3-trimethylsilyloxy-1-butene
  参考文献：
  名称：

  TTMPP催化的三氟甲基硅烷对羰基化合物和亚胺的三氟甲基化

  摘要：

  高碱性膦，三（2,4,6-三甲氧基苯基）膦（TTMPP）使用三氟甲基三甲基硅烷催化三氟甲基化，以羰基化合物和亚胺的高至高收率得到相应的三氟甲基化产物。

  DOI：

  10.1016/j.tetlet.2008.05.053

文献信息

• Lewis Base-Catalyzed Perfluoroalkylation of Carbonyl Compounds and Imines with (Perfluoroalkyl)trimethylsilane
  作者：Yoshikazu Kawano、Nobuya Kaneko、Teruaki Mukaiyama

  DOI：10.1246/bcsj.79.1133

  日期：2006.7

  Lewis base-catalyzed perfluoroalkylation of carbonyl compounds and aldimines with (perfluoroalkyl)trimethylsilanes (TMSCF3, TMSC2F5, and TMSC3F7) is described. The nitrogen- or oxygen-containing an...

  描述了路易斯碱催化羰基化合物和醛亚胺与（全氟烷基）三甲基硅烷（TMSCF3、TMSC2F5 和 TMSC3F7）的全氟烷基化。含氮或含氧...
• TTMPP-catalyzed trifluoromethylation of carbonyl compounds and imines with trifluoromethylsilane
  作者：Satoru Matsukawa、Marina Saijo

  DOI：10.1016/j.tetlet.2008.05.053

  日期：2008.7

  A highly basic phosphine, tris(2,4,6-trimethoxyphenyl)phosphine (TTMPP), catalyzes trifluoromethylation using trifluoromethyltrimethylsilane to give the corresponding trifluoromethylated products in good to high yields, with both carbonyl compounds and imines.

  高碱性膦，三（2,4,6-三甲氧基苯基）膦（TTMPP）使用三氟甲基三甲基硅烷催化三氟甲基化，以羰基化合物和亚胺的高至高收率得到相应的三氟甲基化产物。
• Lithium Acetate-catalyzed Trifluoromethylation of Carbonyl Compounds with (Trifluoromethyl)trimethylsilane
  作者：Teruaki Mukaiyama、Yoshikazu Kawano、Hidehiko Fujisawa

  DOI：10.1246/cl.2005.88

  日期：2005.1

  Trifluoromethylation of various aldehydes and ketones with (trifluoromethyl)trimethylsilane in the presence of a catalytic amount of a Lewis base such as lithium acetate proceeded smoothly to affor...

  在催化量的路易斯碱（如乙酸锂）存在下，各种醛和酮与（三氟甲基）三甲基硅烷的三氟甲基化反应顺利进行，得到...
• CsF-Catalyzed Nucleophilic Trifluoromethylation of <i>trans</i>-Enones with Trimethyl(trifluoromethyl)silane:  A Facile Synthesis of <i>trans</i>-α-Trifluoromethyl Allylic Alcohols
  作者：Rajendra P. Singh、Robert L. Kirchmeier、Jean'ne M. Shreeve

  DOI：10.1021/ol990844r

  日期：1999.10.1

  [GRAPHICS]Reactions of trans-enones, R-C=C-COR' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Pt, CFB) (la-e), with TMS-CF3 in the presence of catalytic amounts of cesium fluoride (CsF) in ethylene glycol dimethyl ether led to the formation of the corresponding trans-alpha-trifluoromethyl silyl ethers, R-C=C-C(OSiMe3)(CF3)R' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Pt, CFB) (2a-e), in essentially quantitative yield. On hydrolysis with aqueous HCl, the corresponding trans-alpha-trifluaromethyl allylic alcohols, R-C=C-C(OH)(CF3)R' (R = Ph, Me, -C=CH-CH=C-S; R' = Ph, Me, Et, CF3) (3a-e), were formed in >90% isolated yield. Under similar reaction conditions, 2-cyclohexen-1-one (1f) also gave trifluoromethyl allylic alcohols (3f) in 92% yield. The intermediates (2a-f) and products (3a-f) are liquids and were characterized by IR, H-1, (19)f and C-13 NMR, MS, and high-resolution mass spectroscopy (HRMS).
• Potassium Alkoxide as an Efficient Catalyst for Nucleophilic Perfluoroalkylation: Attempt at Anion-Controlled Enantioselective Insertion of a Trifluoromethyl Group
  作者：Taiga Yurino、Takeshi Ohkuma、Hiroyuki Yamashita、Yuanrong Shan、Zhen Wu

  DOI：10.1055/a-1914-1518

  日期：2022.10

  Potassium alkoxide was found to be a highly active catalyst for the nucleophilic trifluoromethylation of carbonyl compounds. The catalytic system was successfully applied to the reactions of both aldehydes and ketones, affording the corresponding trifluoromethylated products in high yields at low catalyst loadings (0.1–0.01 mol%) in several solvents, such as THF, toluene, and CH2Cl2. In addition, the

  发现醇钾是羰基化合物的亲核三氟甲基化的高活性催化剂。该催化体系成功地应用于醛和酮的反应，在 THF、甲苯和 CH 2 Cl 2等几种溶剂中以低催化剂负载量（0.1-0.01 mol%）以高产率提供相应的三氟甲基化产物。此外，含有 ( S )-2,2'-双[双(3,5-二甲基苯基)膦基]-1,1'-联萘 [( S )-XylBINAP]的 Ru(II) 络合物的钾盐配体和两个l原位制备的-苏糖酸盐配体催化芳族醛的对映选择性三氟甲基化，尽管 ee 值不令人满意（小于 20%）。