cis-4-Bromomethyl-3-(2,2,2-trichloroethyl)tetrahydrofuran

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: cis-4-Bromomethyl-3-(2,2,2-trichloroethyl)tetrahydrofuran
• 英文别名: cis-3-(bromomethyl)-4-(2,2,2-trichloroethyl)tetrahydrofuran；(3R,4S)-3-(bromomethyl)-4-(2,2,2-trichloroethyl)oxolane
• 化学式: C₇H₁₀BrCl₃O
• 分子量: 296.419
• InChiKey: WRKBMXVTSCYSKL-RITPCOANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  12
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  三氯溴甲烷 、 烯丙基醚 在 三乙基硼 作用下， 以 甲醇 、 水 为溶剂， 生成 trans-4-Bromomethyl-3-(2,2,2-trichloroethyl)tetrahydrofuran 、 cis-4-Bromomethyl-3-(2,2,2-trichloroethyl)tetrahydrofuran
  参考文献：
  名称：

  Triethylborane-Induced Radical Addition of Halogenated Compounds to Alkenes and Alkynes in Water

  摘要：

  用催化量的三乙基硼烷处理水中的δ-碘-δ-丁内酯和苯乙炔混合物，通过分子间自由基加成反应生成相应的加合物，收率很高。三乙基硼烷介导的水介质自由基反应可在酸性或碱性条件下进行。

  DOI：

  10.1055/s-1998-1985

文献信息

• Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings
  作者：Bruce C. Gilbert、Wilhelm Kalz、Chris I. Lindsay、P. Terry McGrail、Andrew F. Parsons、David T. E. Whittaker

  DOI：10.1039/b000835o

  日期：——

  Photolysis of dimanganese decacarbonyl [Mn2(CO)10] using visible light produces the manganese pentacarbonyl radical [·Mn(CO)5] which reacts with organohalides to form carbon-centred radicals. Efficient halogen-atom abstraction occurs with allylic or benzylic halides or polyhalogenated precursors bearing a weak carbon–halogen bond. Steric interactions are also important and primary halides generally react much faster with ·Mn(CO)5 than secondary or tertiary halides. The carbon-centred radicals can undergo efficient dimerisation or, in the presence of an acceptor double bond, cyclisation to form 5-membered rings. Cyclisation of terminal alkenes leads to primary radicals, which can then react by iodine- or bromine-atom transfer or, on addition of propan-2-ol, hydrogen-atom transfer. Hydroxylamines can also be formed when cyclisation reactions are carried out in the presence of TEMPO. These high-yielding cyclisation–trapping reactions are initiated under mild reaction conditions and the manganese halide by-products [of type XMn(CO)5] can be easily separated from products by a simple DBU work-up procedure.

  用可见光光解二锰十羰基化合物 [Mn2(CO)10] 会产生锰五羰基自由基 [·Mn(CO)5]，该自由基与卤代烃反应生成以碳为中心的自由基。与烯丙基或苯甲基卤代物，或具有较弱碳-卤素键的多卤代前驱体，发生高效的卤素原子抽取反应。立体相互作用也很重要，初级卤代物通常比次级或三级卤代物与 ·Mn(CO)5 反应更快。以碳为中心的自由基可以进行高效的二聚反应，或者在存在接受体双键的情况下，环化形成5员环。末端烯烃的环化反应会导致生成初级自由基，随后这些自由基可以通过碘或溴原子转移反应，或者在加入异丙醇的情况下进行氢原子转移反应。当环化反应在TEMPO存在的情况下进行时，还可以形成羟胺。这些高产率的环化-捕捉反应在温和的反应条件下发起，锰卤化物副产物 [类型为 XMn(CO)5] 可以通过简单的DBU后处理程序轻松与产物分离。
• Triethylborane-Induced Radical Addition of Halogenated Compounds to Alkenes and Alkynes in Water
  作者：T. Nakamura、H. Yorimitsu、H. Shinokubo、K. Oshima

  DOI：10.1055/s-1998-1985

  日期：1998.12

  Treatment of a mixture of α-iodo-γ-butyrolactone and phenylacetylene in water with a catalytic amount of triethylborane provided the corresponding adduct in good yield via intermolecular radical addition reaction. The triethylborane-mediated radical reaction in aqueous media could be performed under acidic or basic conditions.

  用催化量的三乙基硼烷处理水中的δ-碘-δ-丁内酯和苯乙炔混合物，通过分子间自由基加成反应生成相应的加合物，收率很高。三乙基硼烷介导的水介质自由基反应可在酸性或碱性条件下进行。
• A Room Temperature Kharasch Reaction Catalyzed by Pd(0) in a Heterogeneous Aqueous System
  作者：Dai Motoda、Hidenori Kinoshita、Hiroshi Shinokubo、Koichiro Oshima

  DOI：10.1002/1615-4169(200206)344:3/4<261::aid-adsc261>3.0.co;2-7

  日期：2002.6

  The palladium-catalyzed Kharasch reaction of alkenes and alkynes is enhanced by the use of a heterogeneous aqueous system, without the use of hydrophilic co-solvents or phase transfer catalysts. The Pd(0)-catalyzed reaction of terminal alkenes with bromotrichloromethane in water goes to completion within 2 h at room temperature, whereas no reaction occurs in benzene otherwise under the same conditions. The Pd(0) catalyst in aqueous me la a so effects the radical addition of iodoperfluoroalkanes toward terminal alkenes and alkynes at room temperature.
• <i>In situ</i> generation of radical initiators using amine-borane complexes for carbohalogenation of alkenes
  作者：Virginie Liautard、Marine Delgado、Boris Colin、Laurent Chabaud、Guillaume Michaud、Mathieu Pucheault

  DOI：10.1039/d1cc06390a

  日期：——

  Atom transfer radical addition of alkyl halides to alkenes was developed using a low amount of a stable initiator, amine borane complexes.

  使用少量稳定引发剂，氨硼烷复合物，开发了卤代烷基向烯烃的原子转移自由基加成反应。