3-bromo-1-(tert-butyldiphenylsilyl)oxy-5-trimethylsilyl-2-penten-4-yne | 360768-07-6

• 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: 3-bromo-1-(tert-butyldiphenylsilyl)oxy-5-trimethylsilyl-2-penten-4-yne
• 英文别名: (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne；(Z)-3-bromo-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-yne；[(Z)-3-bromo-5-[tert-butyl(diphenyl)silyl]oxypent-3-en-1-ynyl]-trimethylsilane
• CAS: 360768-07-6
• 化学式: C₂₄H₃₁BrOSi₂
• 分子量: 471.585
• InChiKey: VTBSKCBTEATVTP-FXBPSFAMSA-N

物化性质

• 沸点：
  468.7±45.0 °C(Predicted)
• 密度：
  1.14±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.72
• 重原子数：
  28
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  3-bromo-1-(tert-butyldiphenylsilyl)oxy-5-trimethylsilyl-2-penten-4-yne 在 锂硼氢 、 cerium(III) chloride 、 1,3-bis[(diphenylphosphino)propane]dichloronickel(II) 、 (Sia)2BH 、 potassium carbonate 、 戴斯-马丁氧化剂 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 丙酮 为溶剂， 反应 32.0h， 生成 (2E,5Z)-(1R)-7-(tert-butyldiphenylsilyl)oxy-1-{(4R,5S)-2,2-dimethyl-5-[2-(4-methoxybenzyloxy)ethyl]-[1,3]-dioxolan-4-yl}-5-methyl-hepta-2,5-dien-1-ol
  参考文献：
  名称：

  Stereoselective preparation of trisubstituted (Z)-alkenes; synthesis of the C17–C27 fragment of (−)-laulimalide

  摘要：

  A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenaI (3), which is coupled with ketophosphonate 4 to give enone 13. The eta-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2' reaction stereoselectively, furnishing a C17-C27 carbon unit of (-)-laulimalide. (C) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.01.002
• 作为产物：
  描述：

  tert-butyldiphenylsilyl 3,3-dibromoprop-2-en-1-yl ether 、 三甲基乙炔基硅 在 (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride copper(l) iodide 、 二异丙胺 作用下， 以 苯 为溶剂， 以81%的产率得到3-bromo-1-(tert-butyldiphenylsilyl)oxy-5-trimethylsilyl-2-penten-4-yne
  参考文献：
  名称：

  1,1-二溴-1-烯烃的逐步交叉偶联反应立体控制支链烯炔的合成

  摘要：

  通过Sonogashira偶联，随后的Sonogashira，Suzuki-Miyaura和Kumada-Tamao-Corriu偶联反应制备了几何上纯净的炔基，烯基和烷基取代的支链炔烃。

  DOI：

  10.1016/s0040-4039(01)00749-3

文献信息

• Stereocontrolled synthesis of branched enyne by stepwise cross-coupling reactions of 1,1-dibromo-1-alkenes
  作者：Jun'ichi Uenishi、Katsuaki Matsui

  DOI：10.1016/s0040-4039(01)00749-3

  日期：2001.6

  Geometrically pure alkynyl, alkenyl and alkyl substituted branched enynes were prepared by the Sonogashira coupling followed by Sonogashira, Suzuki–Miyaura, and Kumada–Tamao–Corriu coupling reactions.

  通过Sonogashira偶联，随后的Sonogashira，Suzuki-Miyaura和Kumada-Tamao-Corriu偶联反应制备了几何上纯净的炔基，烯基和烷基取代的支链炔烃。
• Pd-catalyzed cross-coupling reaction of (Z)- and (E)-bromoenyne: unusual stereochemical outcome
  作者：Jun’ichi Uenishi、Katsuaki Matsui、Masashi Ohmi

  DOI：10.1016/j.tetlet.2004.11.061

  日期：2005.1

  Pd-catalyzed cross-coupling reaction of (E)-bromoenyne 1Z with 1-alkyne and tributylvinyl–stannane occurs with retention of the configuration in benzene but with an inversion of the configuration in DMF or CH2Cl2. On the other hand, that of (Z)-bromoenyne 1E occurs with retention of the configuration in these solvents.

  （E）-溴代炔1 Z与1-炔烃和三丁基乙烯基-锡烷的Pd催化交叉偶联反应在苯中保留构型，而在DMF或CH 2 Cl 2中发生构型反转。另一方面，（Z）-溴代炔1 E的构型在这些溶剂中保持不变。
• Studies on stereoselective Sonogashira coupling of 1,1-dibromo-1-alkene
  作者：Jun'ichi Uenishi、Katsuaki Matsui、Hirohisa Ohmiya

  DOI：10.1016/s0022-328x(02)01262-7

  日期：2002.7

  The stercoselective Sonogashira coupling of 1,1-dibromo-l-alkene was described. The use of PdCl2(dppf) as a catalyst with trialkylsilylacetylene in benzene selectively gave the (Z)-bromoenyne (2a) along with small amounts of the enediyne (3a). Based on the experimental results, a mechanism of the selectivity was proposed. The bromoenyne was coupled with some electrophiles to give the substituted (Z)-bromoenynes after deprotection. of the terminal silyl group. (C) 2002 Elsevier Science B.V. All rights reserved.
• Trienylboronic acid, a versatile coupling tool for retinoid synthesis; stereospecific synthesis of 13-aryl substituted (11Z)-retinal
  作者：Jun'ichi Uenishi、Katsuaki Matsui、Akimori Wada

  DOI：10.1016/s0040-4039(03)00550-1

  日期：2003.4

  Trienylboronic acid 1a was prepared from iodotriene 3, which was coupled with (2Z,4Z)-3-aryl-5-iodo-2,4-pentadienol 9 by Suzuki coupling reaction to give geometrically pure 13-aryl substituted (11Z)-retinol 10. Oxidation of 10 gave 13-aryl substituted (11Z)-retinal 11. (C) 2003 Elsevier Science Ltd. All rights reserved.
• Stereoselective preparation of trisubstituted (Z)-alkenes; synthesis of the C17–C27 fragment of (−)-laulimalide
  作者：Jun'ichi Uenishi、Masashi Ohmi、Katsuaki Matsui、Megumi Iwano

  DOI：10.1016/j.tet.2005.01.002

  日期：2005.2

  A Ni-catalyzed cross-coupling reaction of (Z)-5-(tert-butyldiphenylsilyl)oxy-3-bromo-1-trimethylsilyl-3-penten-1-yne (1) with alkyl Grignard reagent gives (Z)-3-alkyl-5-(tert-butyldiphenylsilyl)oxy-1-trimethylsilyl-3-penten-1-ynes (2) stereospecifically in good yields. The (Z)-enyne 2a is transformed in four steps to (Z)-3-methyl-5-silyloxy-3-pentenaI (3), which is coupled with ketophosphonate 4 to give enone 13. The eta-hydroxyallyl methanesulfonate derived from 13 is cyclized to 3,6-dihydro[2H]pyran by an intramolecular SN2' reaction stereoselectively, furnishing a C17-C27 carbon unit of (-)-laulimalide. (C) 2005 Elsevier Ltd. All rights reserved.