bromotriisopropoxytitanium | 57833-68-8

• 分子结构分类: 有机化合物
• 英文名称: bromotriisopropoxytitanium
• 英文别名: BrTi(OiPr)3；TiBr(OiPr)3；Bromotitanium(3+);propan-2-olate
• CAS: 57833-68-8
• 化学式: C₉H₂₁BrO₃Ti
• 分子量: 305.048
• InChiKey: PCIDPLXTTQZJIH-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  14.0
• 可旋转键数：
  6.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.69
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  四甲基铵(1-羟基亚乙基)五羰基铬 、 bromotriisopropoxytitanium 以 二氯甲烷 为溶剂， 以>99的产率得到
  参考文献：
  名称：

  Structure and bonding of heterobimetallic Fischer carbene complexes

  摘要：

  Heterobimetallic Fischer carbene complexes (CO)5CrC(OM')(R) [M' = Ti(O-iPr)3, R = n-Bu (3); R = 2-furyl (4); R = C(Me)CH2 (5); M' = TiCp2Cl, R = C(Me)CH2 (6)] are readily synthesized by metalation of pentacarbonylchromium acylate intermediates. X-ray crystallographic determinations have been performed at -120-degrees-C for these compounds, as well as for the acylate precursor [NMe4][(CO)5CrC(O)-(CMeCH2)] (7). Structures of 3-5 are the first to be reported of bimetallic carbene systems in which the Lewis acidic metal contains only oxygen ligands. The heterobimetallic complexes display unusually short Cr-C(carbene) and O-C(carbene) bond distances, with respect to standard alkoxycarbene analogues. 3 is monoclinic, P2(1)/n, with a = 12.694 (2) angstrom, b = 14.409 (3) angstrom, c = 13.552(3) angstrom, beta = 96.12 (2)-degrees, and R = 0.044. 4 is monoclinic, P2(1)/n, with a = 12.431 (4) angstrom, b = 10.775 (2) angstrom, c = 17.476 (6) angstrom, beta = 95.17 (3)-degrees, and R = 0.046. 5 is triclinic, P1BAR, with a = 9.555 (2) angstrom, b = 11.135 (3) angstrom, c = 12.613 (4) angstrom, alpha = 108.33 (2)-degrees, beta = 110.73 (2)-degrees, gamma = 97.51 (2)-degrees, and R = 0.038. 6 is monoclinic, P2(1)/n, with a = 12.369 (3) angstrom, b = 12.964 (3) angstrom, c = 12.993 (4) angstrom, beta = 107.47 (2)-degrees, and R = 0.031. 7 is orthorhombic, Pnma, with a = 11.603 (3) angstrom, b = 9.327 (3) angstrom, c = 14.993 (7) angstrom, and R = 0.039. The relevance of structural and spectroscopic data to bonding in these systems is discussed: the substitution of an O-bound electron-deficient metal for an O-alkyl group of a Fischer alkoxycarbene complex appears to increase pi-electron delocalization across the carbenoxy unit in such a way as to strengthen both M-C(carbene) and O-C(carbene) interactions.

  DOI：

  10.1021/om00038a037
• 作为产物：
  描述：

  titanium(IV) isopropylate 、 溴化钛(IV) 以 二氯甲烷 为溶剂， 生成 bromotriisopropoxytitanium
  参考文献：
  名称：

  烯丙醇的催化对映选择性二溴化

  摘要：

  已经开发了一种新的二溴化反应，涉及将二溴丙二酸作为溴源和溴化钛物种作为溴源的组合。酒石酸衍生的二醇通过明显的配体加速实现了对映选择性催化。

  DOI：

  10.1021/ja4083182
• 作为试剂：
  描述：

  间甲酚 在 叔丁基过氧化氢 、 bromotriisopropoxytitanium 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以78%的产率得到4-溴-3-甲基苯酚
  参考文献：
  名称：

  Transition Metal-Catalyzed Oxidations. 11.Para-selective chlorination and bromination of phenols with tert-butyl hydroperoxide and TiX(OiPr)3

  摘要：

  Mononuclear phenols 1-4 are chlorinated or brominated with high para-selectivity and in good yields to the halides 5-11 with the TiXn(OiPr)(m)/TBHP system (X = Cl or Pr).

  DOI：

  10.1002/(sici)1521-3897(199901)341:1<59::aid-prac59>3.0.co;2-8

文献信息

• Azaphilic versus Carbophilic Coupling at CN Bonds: Key Steps in Titanium-Assisted Multicomponent Reactions
  作者：Torsten Roth、Hubert Wadepohl、Eric Clot、Lutz H. Gade

  DOI：10.1002/chem.201503732

  日期：2015.12.14

  mediated by titanium(IV) alkoxides. The carbo‐ and azaphilic arylation step may be separated by choosing the order in which the two equivalents of aryl transfer reagent are added. In the course of this transformation, the ancillary N‐heterocycle acts as both a directing anchor group and electron reservoir. In the selectivity‐determining step, the selectivity is governed by a choice between (direct) C‐ and

  N-杂环腈的连续C-和N-芳基化是由钛(IV)醇盐介导的。碳芳基化步骤和氮亲芳基化步骤可以通过选择添加两当量芳基转移试剂的顺序来分开。在这个转变过程中，辅助的N-杂环既充当导向锚基团又充当电子库。在选择性确定步骤中，选择性由（直接）C-芳基化和Ti-芳基化之间的选择决定；后者开辟了一条反应途径，允许进一步迁移到氮原子。从反应混合物中分离含金属聚集体和计算研究为反应机理提供了见解。随后，设计了一种多组分一锅法方案来快速访问复杂的季碳中心。
• ?-complexes of transition metals in organic synthesis. 1. cross-coupling of organotitanium compounds with allyl halides in the presence of palladium complexes
  作者：A. N. Kasatkin、A. N. Kulak、G. A. Tolstikov

  DOI：10.1007/bf00959380

  日期：1987.2
• Unexpected diversity in the coordination chemistry of tartrate esters with titanium(IV)
  作者：Steven F. Pedersen、John C. Dewan、Richard R. Eckman、K. Barry Sharpless

  DOI：10.1021/ja00238a065

  日期：1987.2