(Z)-1-trimethylsilyl-3-bromopenta-2,4-diene | 278781-98-9

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 乙烯基卤化物
• 英文名称: (Z)-1-trimethylsilyl-3-bromopenta-2,4-diene
• 英文别名: (Z)-3-bromo-5-trimethylsilylpenta-1,3-diene；(3-bromopenta-2,4-dienyl)trimethylsilane；[(2Z)-3-bromopenta-2,4-dienyl]-trimethylsilane
• CAS: 278781-98-9
• 化学式: C₈H₁₅BrSi
• 分子量: 219.197
• InChiKey: PGJNEIOTKQGTLE-VURMDHGXSA-N

物化性质

• 沸点：
  193.0±23.0 °C(Predicted)
• 密度：
  1.106±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  10
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  氟双(苯基磺酰基)甲烷 、 (Z)-1-trimethylsilyl-3-bromopenta-2,4-diene 在 bis(η3-allyl-μ-chloropalladium(II)) 、 potassium tert-butylate 、 2,2'-双(二苯基磷)联苯 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以85%的产率得到6-fluoro-6,6-bis(phenylsulfonyl)-1-trimethylsilyl-2,3-hexadiene
  参考文献：
  名称：

  使用FBSM通过钯催化的单氟甲基化合成氟化烯。

  摘要：

  使用氟双（苯磺酰基）甲烷（FBSM）作为亲核试剂，钯催化的取代2-溴1,3-二烯的单氟甲基化反应以高收率得到了以前未知的单氟甲基化的异戊烯，这是具有生物学吸引力的艾伦醇的等排体。

  DOI：

  10.1039/b912531k
• 作为产物：
  描述：

  [2,2-Dibromo-3-(trimethylsilylmethyl)cyclopropyl]methyl-trimethylsilane 以75%的产率得到(Z)-1-trimethylsilyl-3-bromopenta-2,4-diene
  参考文献：
  名称：

  3-Bromopentadienylsilane:  A New Reagent for the Introduction of a Functional Pentadienyl Unit with Fixed Configuration

  摘要：

  [GRAPHICS]The (Z)-1-trimethylsilyl-3-bromopenta-2,4-diene 3 was prepared through a sequence involving the reductive silylation of butadiene, dibromocarbene addition on the resulting disilane 1) and thermolytic ring opening. With aldehydes, this new pentadienylsilane reacts exclusively via an S-E" pathway, In the presence of an alcohol or a carbamate under Lewis acid activation, 3 yields, respectively, bromopentadienyl ethers or bromopentadienyl-protected amines.

  DOI：

  10.1021/ol0058137

文献信息

• Effects of Silyl Substituents on the Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl)silanes and Their SE2′ Chirality Transfer Reactions
  作者：Masamichi Ogasawara、Yonghui Ge、Atsushi Okada、Tamotsu Takahashi

  DOI：10.1002/ejoc.201101634

  日期：2012.3

  A series of axially chiral 4-substituted-1-silyl-2,3-butadienes [(allenylmethyl)silanes] were synthesized from 3-bromo-5-silylpenta-1,3-dienes by a Pd-catalyzed asymmetric reaction with a soft nucleophile. The optically active (allenylmethyl)silanes react with an acetal in the presence of TiCl4 to give the enantiomerically enriched 1,3-diene derivatives through an SE2′ pathway. Effects of the silyl

  一系列轴向手性 4-取代-1-甲硅烷基-2,3-丁二烯 [(allenylmethyl) 硅烷] 是由 3-bromo-5-silylpenta-1,3-二烯通过 Pd 催化的不对称反应合成的。亲核试剂。旋光性（烯丙基甲基）硅烷在 TiCl4 存在下与缩醛反应，通过 SE2' 途径得到富含对映异构体的 1,3-二烯衍生物。研究了甲硅烷基对不对称丙二烯合成和随后的SE2'手性转移反应的对映选择性的影响。发现随着 3-bromo-5-silylpenta-1,3-二烯中甲硅烷基的空间体积从 -SiMe3 增加到 -SiiPr3，两种对映选择性过程的对映选择性也提高了。
• Palladium-Catalyzed Asymmetric Synthesis of Axially Chiral (Allenylmethyl)silanes and Chirality Transfer to Stereogenic Carbon Centers in S_E‘ Reactions
  作者：Masamichi Ogasawara、Kazuhito Ueyama、Takashi Nagano、Yoshiyuki Mizuhata、Tamio Hayashi

  DOI：10.1021/ol027291w

  日期：2003.1.1

  [reaction: see text] Novel stereoselective reactions of 4-substituted-1-trimethylsilyl-2,3-butadienes ((allenylmethyl)silanes) were developed. The axially chiral (allenylmethyl)silanes were prepared from (3-bromopenta-2,4-dienyl)trimethylsilane by a Pd-catalyzed asymmetric reaction with soft nucleophiles with up to 88% enantioselectivity. The (allenylmethyl)silanes reacted with acetals in the presence

  [反应：见正文]开发了4-取代的-1-三甲基甲硅烷基-2,3-丁二烯（（烯丙基甲基）硅烷）的新型立体选择性反应。轴向手性（烯丙基甲基）硅烷是由（3-溴戊-2,4-二烯基）三甲基硅烷通过Pd催化的不对称反应与柔软的亲核试剂以高达88％的对映选择性制备的。（烯丙基甲基）硅烷在TiCl（4）助催化剂的存在下与缩醛反应，通过S（E）'途径生成1,3-二烯衍生物。1,3-二烯基产物仅具有（E）-几何形状，并且在S（E）'反应中观察到高达88％（）（）手性从轴向手性亚烯基转移到中心手性1,3-二烯。
• Unusual Transposition of Allenic Framework in Intramolecular Cyclization of Acetal-Tethered (Allenylmethyl)silanes
  作者：Masamichi Ogasawara、Atsushi Okada、Hidetoshi Murakami、Susumu Watanabe、Yonghui Ge、Tamotsu Takahashi

  DOI：10.1021/ol901780d

  日期：2009.9.17

  Treatment of acetal-tethered (allenylmethyl)silanes, which were obtained from the corresponding 3-bromo-5-silyl-1,3-pentadienes by a Pd-catalyzed reaction with an acetal-tethered malonate, with TiCl4 gave not only vinylcyclohexene derivatives via a standard S(E)2' pathway but also unusual allenylcyclopentane species via cyclization at the delta-position. Deuterium-labeling experiments revealed participation of a 1,2-hydride shift in a carbocation intermediate for the formation of the latter products.
• Synthesis of fluorinated allenes via palladium-catalyzed monofluoromethylation using FBSM
  作者：Masamichi Ogasawara、Hidetoshi Murakami、Tatsuya Furukawa、Tamotsu Takahashi、Norio Shibata

  DOI：10.1039/b912531k

  日期：——

  Palladium-catalyzed monofluoromethylation of substituted 2-bromo-1,3-dienes using fluorobis(phenylsulfonyl)methane (FBSM) as a pronucleophile gave previously unknown monofluoromethylated allenes in high yields, which are the isosteres of biologically attractive allenic alcohols.

  使用氟双（苯磺酰基）甲烷（FBSM）作为亲核试剂，钯催化的取代2-溴1,3-二烯的单氟甲基化反应以高收率得到了以前未知的单氟甲基化的异戊烯，这是具有生物学吸引力的艾伦醇的等排体。
• 3-Bromopentadienylsilane:  A New Reagent for the Introduction of a Functional Pentadienyl Unit with Fixed Configuration
  作者：Maryline Roux、Maurice Santelli、Jean-Luc Parrain

  DOI：10.1021/ol0058137

  日期：2000.6.1

  [GRAPHICS]The (Z)-1-trimethylsilyl-3-bromopenta-2,4-diene 3 was prepared through a sequence involving the reductive silylation of butadiene, dibromocarbene addition on the resulting disilane 1) and thermolytic ring opening. With aldehydes, this new pentadienylsilane reacts exclusively via an S-E" pathway, In the presence of an alcohol or a carbamate under Lewis acid activation, 3 yields, respectively, bromopentadienyl ethers or bromopentadienyl-protected amines.