1-dimethyl-t-butylsiloxy-2-methylcyclopent-2-ene | 118463-71-1

• 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: 1-dimethyl-t-butylsiloxy-2-methylcyclopent-2-ene
• 英文别名: <(2-methyl-2-cyclopenten-1-yl)oxy>dimethyl(1,1-dimethylethyl)silane；Tert-butyl-dimethyl-(2-methylcyclopent-2-en-1-yl)oxysilane
• CAS: 118463-71-1
• 化学式: C₁₂H₂₄OSi
• 分子量: 212.407
• InChiKey: UFLDXRGRABJXCI-UHFFFAOYSA-N

物化性质

• 沸点：
  220.1±29.0 °C(Predicted)
• 密度：
  0.86±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.12
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 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：

  1-dimethyl-t-butylsiloxy-2-methylcyclopent-2-ene 在 臭氧 作用下， 以 二氯甲烷 为溶剂， 以39%的产率得到tert-Butyl-dimethyl-((1S,2R,5R)-1-methyl-6,7,8-trioxa-bicyclo[3.2.1]oct-2-yloxy)-silane
  参考文献：
  名称：

  The influence of remote heteroatom substituents on the stereoselectivity of cyclopentene ozonolysis

  摘要：

  The stereoselectivity for ozonide formation from cyclopentenes with allylic heteroatom substituents has been examined. Silyl ethers give high selectivity in favor of the exo-substituted ozonide, while esters of 2-cyclopentenol form ozonide mixtures with little stereoselection. Trapping experiments establish that fragmentation of the primary ozonides is highly regioselective to give only one of the isomeric omega-oxo carbonyl oxide intermediates and that the variation in final ozonide stereochemistry results from differing interactions between the remote substituent groups and the carbonyl oxide system during cyclization of this intermediate. The effect of substituent and solvent on ozonide stereochemistry suggests a dominant role for electrostatic repulsion between carbonyl oxide and the heteroatom substituent during intramolecular cycloaddition. A chair-like transition state is proposed for this process and is in accord with the increase in exo selectivity for derivatives of 2-methyl-2-cyclopentenol.

  DOI：

  10.1021/jo00028a059
• 作为产物：
  描述：

  甲基环戊烯醇酮 在 2,6-二甲基吡啶 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 0.58h， 生成 1-dimethyl-t-butylsiloxy-2-methylcyclopent-2-ene
  参考文献：
  名称：

  The influence of remote heteroatom substituents on the stereoselectivity of cyclopentene ozonolysis

  摘要：

  The stereoselectivity for ozonide formation from cyclopentenes with allylic heteroatom substituents has been examined. Silyl ethers give high selectivity in favor of the exo-substituted ozonide, while esters of 2-cyclopentenol form ozonide mixtures with little stereoselection. Trapping experiments establish that fragmentation of the primary ozonides is highly regioselective to give only one of the isomeric omega-oxo carbonyl oxide intermediates and that the variation in final ozonide stereochemistry results from differing interactions between the remote substituent groups and the carbonyl oxide system during cyclization of this intermediate. The effect of substituent and solvent on ozonide stereochemistry suggests a dominant role for electrostatic repulsion between carbonyl oxide and the heteroatom substituent during intramolecular cycloaddition. A chair-like transition state is proposed for this process and is in accord with the increase in exo selectivity for derivatives of 2-methyl-2-cyclopentenol.

  DOI：

  10.1021/jo00028a059

文献信息

• Synthesis of aromatic steroids by palladium(0) coupling and electrocyclic ring closure
  作者：Thomas L. Gilchrist、Richard J. Summersell

  DOI：10.1039/p19880002603

  日期：——

  by an acid-catalysed 1,2 methyl shift. The corresponding cyclopentenol (1d) has been prepared from the bromonaphthalene (6) and 3-(t-butyldimethylsilyloxy)-1-iodocylopentene (7) by palladium(0)-catalysed cross coupling. This cyclises in bromobenzene to give the cyclopentaphenanthrene (5b) and the alcohols (3d) and (3e). The known estrone intermediate (9) has been prepared by oxidation of these alcohols

  用硼氢化钠将萘基环戊烯酮（1a）还原为醇（1c）。当在二甲苯中加热时，它会环化，得到estra-1,3,5（10），8（14），9（11）-pentaen-17-ols（2）。17α-醇（2a）是混合物的主要成分，是纯净的分离产物。当在戊苯中加热环戊醇（1c）时，产物为estra-1,3,5（10），8,14-pentaen-17-ols（3b）和（3c），以及碳氢化合物17 -甲基环戊[ a ]菲（5a）。该化合物可能是由醇（2）或（3）由酸催化的1,2-甲基转移。相应的环戊烯醇（1d）已经通过钯（0）催化的交叉偶联由溴萘（6）和3-（叔丁基二甲基甲硅烷氧基）-1-碘二十二碳戊烯（7）制备。这在溴苯中环化，得到环戊菲（5b）和醇（3d）和（3e）。已知的雌酮中间体（9）已经通过这些醇的氧化制备。
• Rhodium(I)-catalyzed isomerization of siloxycyclopropanes leading to enol silyl ethers and allyl silyl ethers
  作者：Kiyoshi Ikura、Ilhyong Ryu、Akiya Ogawa、Nobuaki Kambe、Noboru Sonoda

  DOI：10.1016/s0040-4039(01)93380-5

  日期：1989.1

  The isomerization of siloxycyclopropanes to enol silyl ethers and allyl silyl ethers was accomplished by using [Rh(CO)2Cl]2 as a catalyst. Regiochemistry with respect to the newly formed double bond of the product was highly dependent on the substitution pattern of cyclopropane ring.

  通过使用[Rh（CO）2 Cl] 2作为催化剂，将甲硅烷氧基环丙烷异构化为烯醇甲硅烷基醚和烯丙基甲硅烷基醚。关于产物的新形成的双键的区域化学高度依赖于环丙烷环的取代模式。
• GILCHRIST, THOMAS L.;SUMMERSELL, RICHARD J., J. CHEM. SOC. PERKIN TRANS. PT I,(1988) N 9, C. 2603-2606
  作者：GILCHRIST, THOMAS L.、SUMMERSELL, RICHARD J.

  DOI：——

  日期：——
• The influence of remote heteroatom substituents on the stereoselectivity of cyclopentene ozonolysis
  作者：William H. Bunnelle、Terry A. Isbell

  DOI：10.1021/jo00028a059

  日期：1992.1

  The stereoselectivity for ozonide formation from cyclopentenes with allylic heteroatom substituents has been examined. Silyl ethers give high selectivity in favor of the exo-substituted ozonide, while esters of 2-cyclopentenol form ozonide mixtures with little stereoselection. Trapping experiments establish that fragmentation of the primary ozonides is highly regioselective to give only one of the isomeric omega-oxo carbonyl oxide intermediates and that the variation in final ozonide stereochemistry results from differing interactions between the remote substituent groups and the carbonyl oxide system during cyclization of this intermediate. The effect of substituent and solvent on ozonide stereochemistry suggests a dominant role for electrostatic repulsion between carbonyl oxide and the heteroatom substituent during intramolecular cycloaddition. A chair-like transition state is proposed for this process and is in accord with the increase in exo selectivity for derivatives of 2-methyl-2-cyclopentenol.