3-methyl-1-methoxy-1-trimethylsilyloxy-1-butene | 84393-13-5

• 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: 3-methyl-1-methoxy-1-trimethylsilyloxy-1-butene
• 英文别名: [(1-Methoxy-3-methylbut-1-en-1-yl)oxy](trimethyl)silane；(1-methoxy-3-methylbut-1-enoxy)-trimethylsilane
• CAS: 84393-13-5
• 化学式: C₉H₂₀O₂Si
• 分子量: 188.342
• InChiKey: QLHGCBNTCOIKMC-UHFFFAOYSA-N

物化性质

• 沸点：
  45 °C(Press: 1 Torr)
• 密度：
  0.858±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.98
• 重原子数：
  12
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-methyl-1-methoxy-1-trimethylsilyloxy-1-butene 在 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 苯亚硒酸 、 双氧水 、 三乙胺 、 zinc dibromide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 119.0h， 生成 (-)-3-methyl-2-<(phenylsulfonyl)methyl>butyl chloroacetate
  参考文献：
  名称：

  An enzyme-based synthesis of (S)-(−)-3-methyl-2-[(phenylsiilfonyl)-methyl]butyl phenyl sulfide and the stereochemical course of its alkylation

  摘要：

  The two title reactions have been explored. In the first instance, best results were achieved if the chloroacetate ester of 3-methyl-2[(phenylsulfonyl)methyl]-1-butanol was subjected to enzymatic hydrolysis with lipase P30 (Amano). Subsequent conversion to the sulfide of high optical purity (approximately 95% e.e.) was accomplished by means of tri-n-butylphosphine and diphenyl disulfide. The alkylation of this difunctional intermediate with several electrophiles has proven to be rather impressively diastereoselective. The relative (and absolute) course of these transformations has been established by means of X-ray crystallographic and NMR methods and is rationalized at the mechanistic level.

  DOI：

  10.1016/s0957-4166(00)80137-8
• 作为产物：
  描述：

  异戊酸 在 lithium diisopropyl amide 作用下， 反应 0.5h， 生成 3-methyl-1-methoxy-1-trimethylsilyloxy-1-butene
  参考文献：
  名称：

  quequeques的烷基化组成第三类的羰基化合物。弗里斯特尔艺术与艺术博物馆的利用

  摘要：

  通过Friedal-Crafts反应，通过其烯酮烷基三甲基甲硅烷基乙缩醛对羧酸酯进行t-烷基化反应，可以合成新的高度受阻的化合物。描述了一种在二甲氧基乙烷中使用酰胺钠制备酮的三甲基甲硅烷基醚的新途径。这些化合物的α-叔丁基化可以合成新的拥挤的五取代的酮。研究了该方法的局限性和性能。

  DOI：

  10.1016/s0040-4020(01)92017-4

文献信息

• Sc(OTf)₃-Catalyzed C–C Bond-Forming Reaction of Cyclic Peroxy Ketals for the Synthesis of Highly Functionalized 1,2-Dioxene Endoperoxides
  作者：Haowei Feng、Yukun Zhao、Pengkang Liu、Lin Hu

  DOI：10.1021/acs.orglett.1c00056

  日期：2021.3.5

  A new and general Sc(OTf)3-catalyzed C–C bond-forming reaction of 3-(2-methoxyethoxy)-endoperoxy ketals with silyl ketene acetals, silyl enol ethers, allyltrimethylsilane, and trimethylsilyl cyanide has been developed via the reactive peroxycarbenium ions, affording a wide range of complicated 3,3,6,6-tetrasubstituted 1,2-dioxenes bearing adjacent quaternary carbons and 3-acetyl/allyl/cyano functional

  通过反应性过氧碳鎓，开发了一种新的通用的Sc（OTf）3催化3-（2-甲氧基乙氧基）-内过氧缩酮与甲硅烷基乙烯酮缩醛，甲硅烷基烯醇醚，烯丙基三甲基硅烷和三甲基甲硅烷基氰化物的C–C键形成反应。离子，在室温下以良好的收率提供了多种复杂的带有相邻季碳原子和3-乙酰基/烯丙基/氰基官能团的3,3,6,6-四取代的1,2-二恶烯。值得注意的是，所得的1,2-二氧杂环丁烷在结构上是稳定的，可以在常规加氢条件下从表面转化为另一种重要的1,2-二氧六环内过氧化物，而不会破坏弱的O-O键。
• Reaction of silyl ketene acetals with epoxides: a new method for the synthesis of γ-butanolides
  作者：Veselin Maslak、Radomir Matović、Radomir N. Saičić

  DOI：10.1016/j.tet.2004.07.007

  日期：2004.9

  Titanium tetrachloride promoted reaction of silyl ketene acetals with epoxides, followed by acidic work-up, affords butanolides in moderate/good yields. With epihalohydrins the reaction is regioselective and occurs at the less substituted end of the epoxide; the γ-haloalkyl-γ-butanolides thus obtained can be further transformed into various products.

  四氯化钛促进了甲硅烷基乙烯酮缩醛与环氧化物的反应，然后进行酸性处理，以中等/良好的收率得到丁醇化物。与表卤代醇反应是区域选择性的，发生在环氧化物的取代度较低的末端。由此获得的γ-卤代烷基-γ-丁醇化物可以进一步转化为各种产物。
• (E)-2-ISOPROPYL-5-METHYL-3,5-HEXADIENOATE COMPOUND, METHOD FOR PRODUCING THE SAME, AND METHODS FOR PRODUCING (E)-2-ISOPROPYL-5-METHYL-3,5-HEXADIENOL AND (E)-2-ISOPROPYL-5-METHYL-3,5-HEXADIENYL CARBOXYLATE BY USING THE SAME
  申请人：Shin-Etsu Chemical Co., Ltd.

  公开号：US20170050913A1

  公开（公告）日：2017-02-23

  Provided is a geometrically selective method for producing (±)-(E)-2-isopropyl-5-methyl-3,5-hexadienyl acetate, which is a sex pheromone of grape pineapple mealybug (GPMB). Specifically provided is a method for producing a an (E)-2-isopropyl-5-methyl-3,5-hexadienyl carboxylate compound (4), the method comprising the steps of: dehydrating a 3-hydroxy-2-isopropyl-5-methyl-4-hexenoate compound (1) to obtain an (E)-2-isopropyl-5-methyl-3,5-hexadienoate compound (2); reducing the alkoxycarbonyl group of the compound (2) to obtain (E)-2-isopropyl-5-methyl-3,5-hexadienol (3); and esterifying the compound (3) to obtain the compound (4).

  提供了一种几何选择性方法，用于制备（±）-（E）-2-异丙基-5-甲基-3,5-己二烯基醋酸酯，这是葡萄凤梨介壳虫（GPMB）的性信息素。具体提供了一种制备（E）-2-异丙基-5-甲基-3,5-己二烯酸酯化合物（4）的方法，该方法包括以下步骤：脱水3-羟基-2-异丙基-5-甲基-4-己烯酸酯化合物（1）以获得（E）-2-异丙基-5-甲基-3,5-己二烯酸酯化合物（2）；还原化合物（2）的烷氧羰基以获得（E）-2-异丙基-5-甲基-3,5-己二烯醇（3）；酯化化合物（3）以获得化合物（4）。
• Asymmetric Cycloadditions of <i>o</i>-Quinone Methides Employing Chiral Ammonium Fluoride Precatalysts
  作者：Ethan Alden-Danforth、Michael T. Scerba、Thomas Lectka

  DOI：10.1021/ol802029e

  日期：2008.11.6

  The catalytic, enantioselective, [4 + 2] cycloaddition reaction of ortho-quinone methides with silyl ketene acetals is described. This mechanistically interesting reaction, initiated by a chiral cinchona alkaloid-derived ammonium fluoride "precatalyst" complex, affords a variety of alkyl- and aryl-substituted 3,4-dihydrocoumarin products in excellent yield and with good enantioselectivity.

  描述了邻醌甲基化物与甲硅烷基乙烯酮缩醛的催化，对映选择性[4 + 2]环加成反应。由手性金鸡纳生物碱衍生的氟化铵“预催化剂”络合物引发的该机理有趣的反应以优异的收率和良好的对映选择性提供了多种烷基和芳基取代的3,4-二氢香豆素产物。
• Synthesis and Isolation of α-Oxo Sulfines
  作者：Theodorus J. G. Damen、Binne Zwanenburg

  DOI：10.1080/10426509708545528

  日期：1997.1.1

  The synthesis of several α-oxo sulfines is discribed. Various α-oxo sulfines can be isolated as such. The Diels-Alder reaction of these sulfines with 1,3-dienes can be catalyzed by Lewis acids.

  描述了几种α-氧代亚砜的合成。各种α-氧代亚砜可以这样分离。这些亚砜与 1,3-二烯的 Diels-Alder 反应可以由路易斯酸催化。