rac-cis-1,6-trans-8-bromomethyl-7-oxabicyclo[4.3.0]nonane

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并呋喃
• 英文名称: rac-cis-1,6-trans-8-bromomethyl-7-oxabicyclo[4.3.0]nonane
• 英文别名: 3a,7a-cis-2-(bromomethyl)octahydrobenzofuran；8-(bromomethyl)-7-oxabicyclo[4.3.0]-nonane；8-bromomethyl-7-oxabicyclo[4.3.0]nonane；(2R,3aS,7aS)-2-(bromomethyl)-2,3,3a,4,5,6,7,7a-octahydro-1-benzofuran
• 化学式: C₉H₁₅BrO
• 分子量: 219.121
• InChiKey: ZTDZGIFCWDAJSS-YIZRAAEISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• 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：

  1-phenyl-4-penten-1-ol 在 三氯溴甲烷 、 1,4-环己二烯 、 {4-[3,5-bis(trifluoromethyl)phenyl]-4-oxybut-3-en-2-one}-cobalt(II) 作用下， 以 甲苯 为溶剂， 反应 24.0h， 以96%的产率得到rac-cis-1,6-trans-8-bromomethyl-7-oxabicyclo[4.3.0]nonane
  参考文献：
  名称：

  Reductive and Brominative Termination of Alkenol Cyclization in Aerobic Cobalt-Catalyzed Reactions

  摘要：

  Tetrahydrofur-2-ylmethyl radicals were stereoselectively generated from substituted pent-4-en-1-ols in aerobic cobalt(II)-catalyzed oxidations. Intermediates were trapped with cyclohexa-1,4-diene, gamma-terpinene, BrCCl3, diethyl dibromomalonate, or electron-deficient olefins such as acrylonitrile or dimethyl fumarate to afford functionalized tetrahydrofurans in synthetically useful yields.

  DOI：

  10.1021/ja904577c

文献信息

• Annulated and bridged tetrahydrofurans from alkenoxyl radical cyclization
  作者：Christine Schur、Harald Kelm、Thomas Gottwald、Arne Ludwig、Rainer Kneuer、Jens Hartung

  DOI：10.1039/c4ob01266f

  日期：——

  radicals sharing two or more carbon atoms with a cycloalkane cyclize in a predictable manner stereoselectively and regioselectively to afford in solutions of bromotrichloromethane cycloalkyl-fused or -bridged 2-bromomethyltetrahydrofurans in up to 95% yield. Stereoselectivity in alkenoxyl radical ring closures arises from cumulative steric effects. The substituent positioned the closest to the alkene carbon

  与环烷烃共享两个或更多个碳原子的4-戊氧基自由基以可预测的方式立体选择性和区域选择性地环化，从而在溴三氯甲烷中的环烷基稠合的或桥连的2-溴甲基四氢呋喃溶液中的产率高达95％。烷氧基自由基闭环中的立体选择性是由累积的空间效应引起的。位置最接近烯烃碳的取代基受到氧自由基的攻击，发挥了最强的立体定向作用。这主要电感指南5-外-cyclization 2,3-反式-或2,4-顺式-选择性。远离受攻击的π键的取代基是次级电感器。相对变压器中的次级电感-配置增强了初级电感器的立体声分化；一个顺式-构型次级电感器降低这种效果。次级电感器不能推翻类似尺寸的初级电感器的引导效果。分子内的4-戊烯氧基基团向环己烯键合的外亚甲基基团或环内双键的加成是顺式进行的，这是由非对映体纯的溴代双环[2.2.1]庚基环化的四氢呋喃从动木基乙氧基基团合成而来的。根据理论，烷氧基自由基环化成环内π键的实验性2,3-顺式特异性来自与2
• Efficiency of alkoxyl radical product formation from 5-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones
  作者：Jens Hartung、Christine Schur、Irina Kempter、Thomas Gottwald

  DOI：10.1016/j.tet.2009.11.113

  日期：2010.2

  In a comparative study, reactions between 5-(p-methoxyphenyl)-substituted 3-alkoxy-4-methylthiazole-2(3H)-thiones and appropriate mediators (BrCCl3, Bu3SnH) provided higher yields of alkoxyl radical products (δ-bromohydrins, cyclic ethers, carbonyl compounds) than respective transformations of 5-phenyl- and 5-methyl-substituted derivatives. The unusual selectivity of applied thiohydroxamates to furnish

  在一项比较研究中，由5-（对甲氧基苯基）取代的3-烷氧基-4-甲基噻唑-2（3 H）-硫酮与适当的介体（BrCCl 3，Bu 3 SnH ）之间的反应提供了更高产率的烷氧基自由基产物（ δ-溴代醇，环醚，羰基化合物）分别取代了5-苯基和5-甲基取代的衍生物。即使使用软碳亲电试剂处理，硫代异羟肟酸酯提供O-烷基化产物的选择性也很差，而且3-烷氧基-5-（对甲氧基苯基）-4-甲基噻唑-2（3 H）的显着倾向硫酮结晶，以值得注意的方式促进了新的烷氧基自由基前体家族的制备和纯化。
• <i>N</i>-Alkoxy-4-methyl-5-(<i>p</i>-anisyl)thiazole-2(3<i>H</i>)thiones - New Precursors for Visible Light- or Thermally-Induced Alkoxyl Radical Reactions in Synthesis
  作者：Jens Hartung、Thomas Gottwald、Kristina Špehar

  DOI：10.1055/s-2003-36794

  日期：——

  Visible light-initiated or thermally induced N-O homolysis of hitherto unknown 4-methyl-5-(p-anisyl)-substituted N-alkoxythiazolethiones furnishes alkoxyl radicals, which have been applied in the diastereoselective synthesis of bicyclic tetrahydrofuran rac-5 (5-exo-trig cyclization), formation of erythrose derivative 8 (β-C,C cleavage), and the preparation of bromoalcohol 10 (via selective 1,5-H-translocation)

  迄今为止未知的 4-甲基-5-(对茴香基)-取代的 N-烷氧基噻唑硫酮的可见光引发或热诱导 NO 均裂提供烷氧基自由基，其已应用于双环四氢呋喃 rac-5 (5-exo) 的非对映选择性合成-trig 环化），赤藓糖衍生物 8 的形成（β-C，C 裂解），以及溴醇 10 的制备（通过选择性 1,5-H-易位），可选地在无锡条件下。
• Reductive and Brominative Termination of Alkenol Cyclization in Aerobic Cobalt-Catalyzed Reactions
  作者：Dominik Schuch、Patrick Fries、Maike Dönges、Bárbara Menéndez Pérez、Jens Hartung

  DOI：10.1021/ja904577c

  日期：2009.9.16

  Tetrahydrofur-2-ylmethyl radicals were stereoselectively generated from substituted pent-4-en-1-ols in aerobic cobalt(II)-catalyzed oxidations. Intermediates were trapped with cyclohexa-1,4-diene, gamma-terpinene, BrCCl3, diethyl dibromomalonate, or electron-deficient olefins such as acrylonitrile or dimethyl fumarate to afford functionalized tetrahydrofurans in synthetically useful yields.