diisopropoxy(η2-propene) titanium(II) complex | 852359-08-1

• 分子结构分类: 有机化合物 - 有机硫化合物
• 英文名称: diisopropoxy(η2-propene) titanium(II) complex
• 英文别名: diisopropoxy(η2-propene)titanium；(η2-propene)Ti(O-i-Pr)2；[Ti(η2-propene)(OiPr)2]；(η(2)-propene)Ti(O-i-Pr)2；propan-2-olate;prop-1-ene;titanium(2+)
• CAS: 852359-08-1；169123-69-7
• 化学式: C₉H₂₀O₂Ti
• 分子量: 208.137
• InChiKey: PPVJQIIELFTSDE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  None
• 重原子数：
  None
• 可旋转键数：
  None
• 环数：
  None
• sp3杂化的碳原子比例：
  None
• 拓扑面积：
  None
• 氢给体数：
  None
• 氢受体数：
  None

反应信息

• 作为反应物：
  描述：

  diisopropoxy(η2-propene) titanium(II) complex 、 allenyldimethyl(phenyl)silane 以 not given 为溶剂， 生成
  参考文献：
  名称：

  Coupling reaction of terminal allenes with themselves or acetylenes mediated by (η2-propene)Ti(OPri)2: some new selectivities and synthetic application

  摘要：

  单独处理丙二烯或用(β2-丙烯)Ti(O-i-Pr)2 乙炔处理生成新的钛环，它与一些亲电子试剂反应，得到有机合成有用的中间体。

  DOI：

  10.1039/a706998g
• 作为产物：
  描述：

  titanium tetra-n-propoxide 在 C₃H₇MgBr 作用下， 以 neat (no solvent) 为溶剂， 生成 diisopropoxy(η2-propene) titanium(II) complex
  参考文献：
  名称：

  Intramolecular carbometalation of functionalized terminal alkynes via low-valent titanium complexes

  摘要：

  使用二异丙氧基（η2-丙烯）钛处理带有δ-和γ-官能化的单取代炔烃，可诱导发生分子内环化反应，从而高总体收率地得到4元和5元环烷醇。

  DOI：

  10.1039/b005027j
• 作为试剂：
  描述：

  methyl 5-(trimethylsilyl)-4-pentynyl ketone 在 diisopropoxy(η2-propene) titanium(II) complex 、 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 反应 0.17h， 生成 (+/-)-5-methyl-2-(trimethylsilyl)-1-bicyclo[3.3.0]octen-3-one
  参考文献：
  名称：

  Ti（II）醇盐介导的三取代烯烃底物的串联环化反应不对称合成具有角取代基的双环酮

  摘要：

  [反应：参见正文]通过Ti（II）醇盐介导的开链底物的串联环化反应制备了高达94％ee的角取代的旋光双环酮，即具有三取代双键的8-苯基薄荷基烯酸酯。

  DOI：

  10.1021/ol9904038

文献信息

• Intramolecular Cyclization of 2,7- or 2,8-Bis-unsaturated Esters Mediated by (η²-Propene)Ti(O-<i>i</i>-Pr)₂. Facile Construction of Mono- and Bicyclic Skeletons with Stereoselective Introduction of a Side Chain. A Synthesis of <i>d</i>-Sabinene
  作者：Hirokazu Urabe、Ken Suzuki、Fumie Sato

  DOI：10.1021/ja9716160

  日期：1997.10.1

  tert-Butyl 2-en-7-ynoate 6 was treated with (η2-propene)Ti(O-i-Pr)2 (3), generated in situ from Ti(O-i-Pr)4 or Ti(O-i-Pr)3Cl and i-PrMgCl, in ether at −50 to −20 °C to afford the product 8 in good yield. The presence of the intermediate titanabicycle 7 was verified by bis-deuterolysis with excess D2O. When the titanabicycle 7 was treated with 1.1 equiv of i-PrOD and then worked up as usual, the monodeuterated

  叔丁基 2-en-7-ynoate 6 用 (η2-propene)Ti(Oi-Pr)2 (3) 处理，由 Ti(Oi-Pr)4 或 Ti(Oi-Pr)3Cl 和i-PrMgCl，在-50至-20°C的乙醚中以良好的产率提供产物8。中间体钛双环 7 的存在通过用过量 D2O 进行双氘分解来验证。当钛双环 7 用 1.1 当量的 i-PrOD 处理然后照常处理时，得到了具有高位点选择性和立体选择性的单氘化产物 10。其他亲电子试剂如醛和酮也以高度立体选择性的方式与钛双环反应，得到具有立体定义侧链的环戊烷。相反，在相同条件下用 3 处理相应的乙酯，8-（三甲基甲硅烷基）-（E）-2-辛烯-7-炔酸乙酯（28），然后加入 1。1当量的s-BuOH以80%的产率提供2-(三甲基甲硅烷基)-1-双环[3.3.0]辛烯-3-一(32)。用 i-PrOD、EtCHO 和 Et2CO 代替 s-BuOH 淬灭相同的反应混合物
• Intramolecular Coupling of Vinyl Ether and Olefins or Acetylenes with Ti(II) Reagent. Regio- and Stereo-selective Vinyltitanation of Carbon-Carbon Multiple Bonds
  作者：Ryota Nakajima、Hirokazu Urabe、Fumie Sato

  DOI：10.1246/cl.2002.4

  日期：2002.1

  Treatment of m-alkenyl (or m-alkynyl) vinyl ethers (m = 3,4) with a Ti(II) reagent generated most likely bicyclic oxatitanacycles, which eliminate the alkoxide tether to effect the selective vinyltitanation of the alkene or alkyne moiety to give m-vinyl-1-alkanols or m-vinyl-m-alken-1-ols.

  用 Ti(II) 试剂处理间链烯基（或间炔基）乙烯基醚（m = 3,4）最有可能产生双环氧杂钛环，它消除了醇盐系链以实现烯烃或炔烃部分的选择性乙烯基钛化给出 m-vinyl-1-alkanols 或 m-vinyl-m-alken-1-ols。
• Chemo- and Regioselective Alkylation of Pyridine <i>N</i>-Oxides with Titanacyclopropanes
  作者：Li-Chen Xu、Xiao-Di Ma、Kun-Ming Liu、Xin-Fang Duan

  DOI：10.1021/acs.orglett.3c03469

  日期：2023.12.8

  herein they react preferentially with pyridine N-oxide to accomplish C2–H alkylation beyond these functionalities with double regioselectivity. After being pyridylated at the less hindered C–Ti bond, the remaining C–Ti bond of titanacyclopropanes can be further functionalized by various electrophiles, allowing facile introduction of complex alkyls onto the C2 of pyridines. Its synthetic potential has been

  虽然环丙烷钛主要用于与酯、酰胺和氰基反应进行环丙烷化，但在此它们优先与吡啶N-氧化物反应以完成除这些官能团之外的具有双区域选择性的C2-H烷基化。在受阻较小的 C-Ti 键处被吡啶基化后，环丙烷中剩余的 C-Ti 键可以通过各种亲电子试剂进一步官能化，从而可以轻松地将复杂的烷基引入到吡啶的 C2 上。其合成潜力已通过药物的后期多样化得到证明。
• A Novel Tandem Cyclization of 2,7- or 2,8-Bis-Unsaturated Esters Mediated by (η²-Propene)TiX₂ (X = Cl or O-<i>i</i>-Pr). A Facile Construction of Bicyclo[3.3.0]octane, -[4.3.0]nonane, and -[3.1.0]hexane Skeletons
  作者：Ken Suzuki、Hirokazu Urabe、Fumie Sato

  DOI：10.1021/ja961928n

  日期：1996.1.1
• Efficient and Practical Method for Synthesizing N-Heterocyclic Compounds Using Intramolecular Nucleophilic Acyl Substitution Reactions Mediated by Ti(O-<i>i</i>-Pr)₄/2<i>i</i>-PrMgX Reagent. Synthesis of Quinolones, Pyrroles, Indoles, and Optically Active N-Heterocycles Including Allopumiliotoxin Alkaloid 267A
  作者：Sentaro Okamoto、Masayuki Iwakubo、Katsushige Kobayashi、Fumie Sato

  DOI：10.1021/ja970810j

  日期：1997.7.1

  Treatment of N-(2- or 3-alkynyl)amino esters with a low-valent titanium reagent diisopropoxy(eta(2)-propene)titanium (1), generated in situ by the reaction of Ti(O-i-Pr)(4) and 2i-PrMgCl, resulted in an intramolecular nucleophilic acyl substitution (INAS) reaction to afford alpha-alkylidene-pyrrolidinones or -piperidinones. Thus, treatment of N-propargyl-anthranilates 5, -indole-2-carboxylates 10, or -pyrrole-2-carboxylates 13 with 1 gave 4-quinolones 7, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. Similarly, N-alkynylated alpha- or beta-amino esters 14 or 15 with 1 afforded N-heterocycles 18 or 19. In the reaction of N-(2- or 3-alkenyl)amino esters with 1, the resulting INAS product underwent intramolecular carbonyl addition (ICA) reaction to afford the N-heterocyclic compounds having a cyclopropanol moiety in good to excellent yields. Thus, the treatment of N-alkenyl-anthranilate 4a, -indole-2-carboxylates 8 and 9, or -pyrrole-2-carboxylates 11 and 12 with 1 gave the corresponding quinoline derivative 6a, [1,2-a]indoles, or [1,2-a]pyrroles, respectively. The optically active N-heterocyclic compounds 20 and 21 were obtained from N-alkenylated alpha- or beta-amino esters 16 or 17. A highly efficient total synthesis of allopumiliotoxin alkaloid 267A has also been accomplished. Thus, the N-propargyl-2[(1-hydroxy-1-methoxycarbonyl)ethyl]pyrrolidine 24 (from L-proline in six steps) reacted with 1 to afford the corresponding indolidinone 25 in 67% yield, which has previously been converted to allopumiliotoxin 267A.