(E)-tert-butyl((4-chlorobut-2-en-1-yl)oxy)dimethylsilane | 159428-66-7

• 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: (E)-tert-butyl((4-chlorobut-2-en-1-yl)oxy)dimethylsilane
• 英文别名: tert-butyl-[(E)-4-chlorobut-2-enoxy]-dimethylsilane
• CAS: 159428-66-7
• 化学式: C₁₀H₂₁ClOSi
• 分子量: 220.815
• InChiKey: GVMKGJGEWZQVTQ-VOTSOKGWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  (E)-tert-butyl((4-chlorobut-2-en-1-yl)oxy)dimethylsilane 在 2,2'-联吡啶 、 iron(III)-acetylacetonate 、 三乙基铝 sodium hydride 作用下， 以 四氢呋喃 、 二甲基亚砜 、 甲苯 为溶剂， 反应 24.25h， 生成 3-[(E)-2-(tert-Butyl-dimethyl-silanyloxy)-vinyl]-4-((Z)-propenyl)-cyclopentane-1,1-dicarboxylic acid diethyl ester
  参考文献：
  名称：

  Catalytic Iron-Mediated Triene Carbocyclizations: Stereoselective Five-Membered Ring Forming Carbocyclizations

  摘要：

  The full details of investigations into the regiochemistry and stereochemistry of iron-catalyzed carbocyclizations of 2,7,9-decatriene derivatives to form five-membered carbocyclic ring systems are described. The roles of the allylic substituent, the alkene geometry, diene substitution, and the influence of resident stereogenic centers incorporated in the tether chain connecting the reacting 1,3-diene and alkene subunits are discussed.

  DOI：

  10.1021/jo00102a016
• 作为产物：
  描述：

  (E)-4-(叔丁基二甲基甲硅烷基氧基)-2-丁烯-1-醇 在 四氯化碳 、 potassium carbonate 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 反应 12.0h， 以76%的产率得到(E)-tert-butyl((4-chlorobut-2-en-1-yl)oxy)dimethylsilane
  参考文献：
  名称：

  Catalytic Iron-Mediated Triene Carbocyclizations: Stereoselective Five-Membered Ring Forming Carbocyclizations

  摘要：

  The full details of investigations into the regiochemistry and stereochemistry of iron-catalyzed carbocyclizations of 2,7,9-decatriene derivatives to form five-membered carbocyclic ring systems are described. The roles of the allylic substituent, the alkene geometry, diene substitution, and the influence of resident stereogenic centers incorporated in the tether chain connecting the reacting 1,3-diene and alkene subunits are discussed.

  DOI：

  10.1021/jo00102a016

文献信息

• C–N Bond Formation from Allylic Alcohols via Cooperative Nickel and Titanium Catalysis
  作者：S. Hadi Nazari、Norma Tiempos-Flores、Kelton G. Forson、Jefferson E. Bourdeau、David J. Michaelis

  DOI：10.1021/acs.joc.8b01474

  日期：2018.9.7

  Amination of allylic alcohols is facilitated via cooperative catalysis. Catalytic Ti(O-i-Pr)4 is shown to dramatically increase the rate of nickel-catalyzed allylic amination, and mechanistic experiments confirm activation of the allylic alcohol by titanium. Aminations of primary and secondary allylic alcohols are demonstrated with a variety of amine nucleophiles. Diene-containing substrates also cyclize

  通过协同催化促进烯丙基醇的胺化。催化性Ti（O - Pr）4可以显着提高镍催化的烯丙基胺化的速率，并且机械实验证实钛可以活化烯丙基醇。用各种胺亲核试剂证明伯和仲烯丙基醇的胺化。含二烯的底物在胺化之前还会环化在烯丙基镍中间体上，生成碳环胺产物。此串联过程仅在我们的协同催化系统下才能实现。
• Grignard allylic substitution catalyzed by imidazol-2-ylidene- and imidazol-4-ylidene-magnesium complexes
  作者：Sentaro Okamoto、Hiroyuki Ishikawa、Yoshimi Shibata、Yu-ichiro Suhara

  DOI：10.1016/j.tetlet.2010.08.067

  日期：2010.10

  imidazolium salts, γ-substituted allyl chlorides reacted with alkyl Grignard reagents to undergo substitution reactions in an SN2′-selective fashion, where the magnesium ate complexes [(N-heterocyclic carbene-MgR3)−(MgX)+] of imidazol-2-ylidenes or imidazol-4-ylidenes, generated in situ, were postulated as the active species. It was observed that the reactions with imidazol-4-ylidene catalysts were faster

  在催化量的1,2-二取代或1,2,3-三取代的咪唑鎓盐的存在下，γ-取代的烯丙基氯与烷基格氏试剂反应，以S N 2'-选择性方式进行取代反应，其中假定将原位生成的咪唑-2-亚胺或咪唑-4-亚胺的镁盐配合物[（N-杂环卡宾-MgR 3）-（MgX）+ ]作为活性物质。观察到与咪唑-4-亚烷基催化剂的反应比与咪唑-2-亚烷基催化剂的反应更快。初步研究了使用手性咪唑盐的对映选择性催化。
• A Cross Metathesis Based Protocol for the Effective Synthesis of Function­alised Allyl Bromides and Chlorides
  作者：Pier Giorgio Cozzi、Achille Umani-Ronchi、Marco Bandini、Sebastiano Licciulli

  DOI：10.1055/s-2004-815936

  日期：——

  Functionalised allyl halides, useful starting materials for the preparation of substituted organometallic reagents can be simply obtained by a straightforward approach. Hoveyda’s ruthenium carbene catalyst 3, used in catalytic amount (2 mol%), is able to promote the cross metathesis of allyl bromide and chloride with a variety of different substituted olefins giving the corresponding functionalised allyl halides in satisfactory yields. trans-Olefins are obtained as major diastereoisomers reaching 90:10 (trans:cis) ratio when allyl chloride is used as the metathesis partner. This reaction represents a simple and accessible way for the preparation of valuable precursors for functionalised organometallic reagents. In particular, the use of functionalised allyl bromides (10b and 13) in the enantioselective Nozaki-Hiyama reaction promoted by [Cr(Salen)Cl] is presented.

  功能化的烯丙基卤化物，作为制备取代有机金属试剂的有用起始材料，可以通过一种直接的方法简单地获得。Hoveyda的钌卡宾催化剂3，以催化量（2 mol%）使用，能够促进烯丙基溴和氯与多种不同取代烯烃的交叉复分解反应，以令人满意的产率得到相应的功能化烯丙基卤化物。使用烯丙基氯作为复分解反应伙伴时，主要得到trans-烯烃的非对映异构体，比例达到90:10（trans:cis）。这一反应为制备功能化有机金属试剂的有价值前体提供了一种简单且易行的方法。特别是，展示了功能化烯丙基溴（10b和13）在[Cr(Salen)Cl]促进的手性选择性野崎-日山反应中的应用。
• Synthesis of Petrosins C and D
  作者：Clayton H. Heathcock、Richard C. D. Brown、Thea C. Norman

  DOI：10.1021/jo9801770

  日期：1998.7.1

  Petrosins C and D (5 and 6), diastereomers of the known natural products petrosin (1), petrosin A (2), and petrosin B (3), have been prepared. The synthetic route involved initial creation of a 16-membered bis-pyridine intermediate, exemplified by compounds 7, 28, and 52. Several different methods for formation of the macrocycle were evaluated, and the most efficient (Schemes 7-9) involved use of Z double bonds in the six-carbon chains linking the two pyridine rings. This approach permitted the two pyridine subunits (37 and 39) to be joined by alkylation of a lithiated alpha-methylpyridine with an allylic chloride (e.g., 37 + 39 --> 40 and 49 --> 45). Bisannulation of compounds 7 and 28 was complicated by a surprising lack of acidity of the a-pyridyl methylene groups. Eventually, this problem was solved by stepwise introduction of two allyl groups, using the more acidic sulfone for introduction of the first (e.g., 52 --> 53) and direct allylation to introduce the second (e.g., 54 --> 55 + 56). The bisannulation was completed by hydroboration and conversion of the primary alcohols into methanesulfonate derivatives, which cyclized to afford bis-pyridinium derivatives. Reduction of these intermediate salts with sodium borohydride provided crystalline bis-enol ethers (60 and 63) and the relative configuration was established by single-crystal X-ray analysis of 63. After hydrolysis of the enol ethers to the corresponding ketones, the syntheses of 5 and 6 were completed by enolate methylation. As expected, compounds 5 and 6 do not form imine derivatives when treated with primary amines, presumably because of A(1,3) strain.
• Catalytic Iron-Mediated Triene Carbocyclizations: Stereoselective Five-Membered Ring Forming Carbocyclizations
  作者：James M. Takacs、Young-Chan Myoung、Lawrence G. Anderson

  DOI：10.1021/jo00102a016

  日期：1994.11

  The full details of investigations into the regiochemistry and stereochemistry of iron-catalyzed carbocyclizations of 2,7,9-decatriene derivatives to form five-membered carbocyclic ring systems are described. The roles of the allylic substituent, the alkene geometry, diene substitution, and the influence of resident stereogenic centers incorporated in the tether chain connecting the reacting 1,3-diene and alkene subunits are discussed.