3-bromo-1-(trimethylsilyl)-1-propene

• 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-(trimethylsilyl)-1-propene
• 英文别名: trimethylsilylallyl bromide；3-Bromo-1-trimethylsilylpropene；3-bromoprop-1-enyl(trimethyl)silane
• 化学式: C₆H₁₃BrSi
• 分子量: 193.159
• InChiKey: CFABRZVNIPAMRX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.81
• 重原子数：
  8
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  exo-α-methylselenoisoborneol 、 3-bromo-1-(trimethylsilyl)-1-propene 以 丙酮 为溶剂， 反应 2.0h， 以94%的产率得到
  参考文献：
  名称：

  通过手性硒鎓叶立烯高立体选择性合成1,2,3-三取代环丙烷的第一个例子

  摘要：

  通过硒化叶立德开发了一种新的策略，该策略以高收率，极好的非对映选择性和极高的对映选择性（高达> 99％ee）（见方案），以高收率选择性合成了手性1,2,3-三取代环丙烷的三种立体异构体。还提出了不对称环丙烷化的可能途径。

  DOI：

  10.1002/chem.200801936
• 作为产物：
  描述：

  3-(trimethylsilyl)allyl alcohol 在 三溴化磷 作用下， 以 四氢呋喃 为溶剂， 生成 3-bromo-1-(trimethylsilyl)-1-propene
  参考文献：
  名称：

  铑催化的两次区域选择性和对映选择性 C-H 激活：手性单苯荧光团的有效策略

  摘要：

  通过手性瞬时导向基团策略，Rh 催化的双重、区域选择性和对映选择性 C-H 活化已被证明具有中等至良好的产率和值得称赞的对映选择性。新合成的手性荧光团表现出良好的光物理性质，包括大的斯托克斯位移、良好的荧光量子产率、水溶液中的聚集诱导发射、固态下的强发射和圆偏振发光，表明作为手性荧光探针或光电器件的巨大潜在应用材料。

  DOI：

  10.1021/acs.orglett.3c03467

文献信息

• Gallium-mediated highly regioselective reactions of trimethylsilylpropargyl bromide and trimethylsilylallyl bromide with carbonyl compounds
  作者：Ying Han、Yao-Zeng Huang

  DOI：10.1016/s0040-4039(00)78562-5

  日期：1994.12

  One-pot reactions of gallium powder, trimethylsilylpropargyl bromide, aldehydes or ketones in the presence of KI and LiCl show very high acetylenic selectivity and under the same conditions, trimethylsilylallyl bromide also exhibits very high selectivity favoring α-adducts.

  镓粉，三甲基甲硅烷基炔丙基溴，醛或酮在KI和LiCl存在下的一锅反应显示出很高的炔属选择性，在相同条件下，三甲基甲硅烷基烯丙基溴也表现出非常高的选择性，有利于α加合物。
• Synthesis of cyclic α-hydrazino acid derivatives via N-acylhydrazonium ions
  作者：F Rutjes

  DOI：10.1016/s0040-4020(01)96267-2

  日期：1993.9.17

  The synthesis of various cyclic α-hydrazino esters is described. The key-step involves an intramolecular reaction of a highly reactive N-acylhydrazonium ion, leading to a cyclic cationic intermediate which either rearranges via an aziridinium ion, or leads to the unrearranged piperazic ester. A deprotection sequence that furnishes the free α-hydrazino acids is detailed.

  描述了各种环状α-肼基酯的合成。关键步骤涉及高反应性N-酰基azo离子的分子内反应，从而导致环状阳离子中间体，该中间体通过叠氮鎓离子重排，或导致未重排的哌嗪酸酯。详细描述了提供游离α-肼基酸的脱保护序列。
• Palladium-Mediated Intramolecular C-N Bond Formation between Tertiary Amines and Alkenes
  作者：Paul A. van der Schaaf、Jean-Pascal Sutter、Mary Grellier、Guido P. M. van Mier、Anthony L. Spek、Gerard van Koten、Michel Pfeffer

  DOI：10.1021/ja00091a016

  日期：1994.6

  The reaction of terminal alkenylarenes having either o-(dimethylamino) or o-[(dimethylamino)methyl] substituents with PdCl2(MeCN)(2) in MeOH in the presence of NaOAc and PPh(3) has been studied. This reaction affords allylic phosphonium compounds for those substrates having more than six carbon atoms between the alkene function and the tertiary amine nitrogen atom, In those cases where the alkene is closer to the NMe(2) unit, this reaction leads, via allylic metalation, to intramolecular cyclization that involves generation of a new C-N bond and results in the formation of cationic 5-, 6-, or 7-membered heterocyclic ammonium compounds. For example, C6H4(CH2CH=CH2)-1-(CHMeNMe(2))-2 can be converted to the endo-cyclization product [C6H4CH=CHCH(2)NMe(2)CH(Me)}-1,2]Cl in 86% yield with this Pd(II)-based system. The cyclization reaction is highly selective and occurs either at the terminal, less substituted olefinic carbon atom (C-gamma), affording ende-cyclization, or at the allylic C-alpha carbon atom, resulting in the formation of exo-cyclic products. The cyclization reaction is thought to proceed via a palladium-assisted C-H activation route: in most cases it was possible to isolate and characterize an eta(3)-allylpalladium complex as a key intermediate and then allow it to react further with PPh(3) to afford a cyclized end product. The X-ray crystal structures of a palladium-allyl complex, i.e., 2i(syn), and a quinolinium derivative, 3a, are described. Crystal data for 2i(syn): monoclinic, space group P2(1)/c, with a = 8.902(1), b = 20.587(1), and c = 9.702(1) Angstrom, beta = 95.52(1)degrees, Z = 4, R = 0.038. Crystal data for 3a: monoclinic, space group P2(1)/n with a = 13.032(1), b = 6.544(1), and c 13.415(1) Angstrom, beta = 114.72(1)degrees, Z = 4, R = 0.042,
• A concise synthesis of (±)-3-deoxyisoaltholactone
  作者：Stephen Philip Fearnley、Pedro Lory

  DOI：10.1016/j.tetlet.2014.07.081

  日期：2014.9
• First Example of Highly Stereoselective Synthesis of 1,2,3-Trisubstituted Cyclopropanes via Chiral Selenonium Ylides
  作者：Hai-Yang Wang、Fei Yang、Xin-Liang Li、Xue-Ming Yan、Zhi-Zhen Huang

  DOI：10.1002/chem.200801936

  日期：2009.4.6

  A new strategy for the highly stereoselective synthesis of three stereoisomers of chiral 1,2,3‐trisubstituted cyclopropanes in good yields with excellent diastereoselectivities and very high enantioselectivities (up to >99 % ee) was developed via selenonium ylides (see scheme). Possible pathways for the asymmetric cyclopropanations were also proposed.

  通过硒化叶立德开发了一种新的策略，该策略以高收率，极好的非对映选择性和极高的对映选择性（高达> 99％ee）（见方案），以高收率选择性合成了手性1,2,3-三取代环丙烷的三种立体异构体。还提出了不对称环丙烷化的可能途径。