(2-环戊烯-1-氧基)二甲基(1,1-二甲基乙基)硅烷 | 68845-73-8

• 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
• 中文名称: (2-环戊烯-1-氧基)二甲基(1,1-二甲基乙基)硅烷
• 英文名称: tert-butyl(cyclopent-2-en-1-yloxy)dimethylsilane
• 英文别名: Tert-butyl-cyclopent-2-en-1-yloxy-dimethylsilane
• CAS: 68845-73-8
• 化学式: C₁₁H₂₂OSi
• 分子量: 198.381
• InChiKey: CLRBSUZPPLTQGO-UHFFFAOYSA-N

物化性质

• 沸点：
  36-38 °C(Press: 1 Torr)
• 密度：
  0.87±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.73
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 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：

  (2-环戊烯-1-氧基)二甲基(1,1-二甲基乙基)硅烷 在 palladium on activated charcoal 吡啶 、 porcine liver esterase 、 4-二甲氨基吡啶 、 氢氧化钾 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 1-(3-二甲基氨基丙基)-3-乙基碳二亚胺 、 N,N-二异丙基乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 phosphate buffer 、 乙醇 、 二氯甲烷 、 二甲基亚砜 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 生成
  参考文献：
  名称：

  Synthesis of a Cyclopentane Amide DNA Analogue and Its Base Pairing Properties

  摘要：

  cpa-DNA monomers containing the bases adenine and thymine have been synthesized starting from the known compound 1 in 12 steps. Partially and fully modified cpa-thymidine and cpa-adenosine containing oligodcoxynucleotides were synthesized by standard oligonucleotide chemistry. Fully modified homo-cpa-A sequences lead to duplex destabilization by -1.4degreesC/mod. relative to DNA. As its congener bca-DNA, cpa-DNA prefers left-handed duplex formation where possible.

  DOI：

  10.1081/ncn-120022837
• 作为产物：
  描述：

  tert-butyl(hepta-1,6-dien-3-yloxy)dimethylsilane 在 Cl₂Ru(=CH-o-O-i-PrC₆H₄)PCy₃ 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以90%的产率得到(2-环戊烯-1-氧基)二甲基(1,1-二甲基乙基)硅烷
  参考文献：
  名称：

  A Recyclable Ru-Based Metathesis Catalyst

  摘要：

  A Ru carbene (8, Scheme 2) that contains an internal metal-oxygen chelate is an active metathesis catalyst and is readily obtained by the sequential treatment of Cl2Ru(PPh3)(3) with (2-isopropoxyphenyl)-diazomethane and PCy3. This Ru-carbene complex offers excellent stability to air and moisture and can be recycled in high yield by silica gel column chromatography. The structures of this and related complexes have been unambiguously established by NMR and single-crystal X-ray diffraction studies.

  DOI：

  10.1021/ja983222u

文献信息

• Use of the 2-Pyridinesulfonyloxy Leaving Group for the Fast Copper-Catalyzed Coupling Reaction at Secondary Alkyl Carbons with Grignard Reagents
  作者：Riku Shinohara、Masao Morita、Narihito Ogawa、Yuichi Kobayashi

  DOI：10.1021/acs.orglett.9b00976

  日期：2019.5.3

  copper-catalyzed coupling reaction of 2-pyridinesulfonates with Grignard reagents revealed that reactions with catalytic Cu(OTf)2 were completed in <40 min. The results differed from those of the previous CuI-catalyzed reactions of tosylates in the presence of additives (LiOMe and TMEDA) for 12–24 h. It was shown that the preferred coordination of the leaving group to the reagents accelerated the reaction

  铜催化的2-吡啶磺酸盐与格利雅试剂的偶联反应研究表明，与催化型Cu（OTf）2的反应在不到40分钟的时间内完成。结果与以前的CuI催化的甲苯磺酸盐在添加剂（LiOMe和TMEDA）存在下12-24小时的反应结果不同。结果表明，离去基团与试剂的优选配位促进了反应。成功的试剂是MeMgCl和其他RMgX。建立了完全反演。
• Oxidation of Olefins into α-Phenylseleno Carbonyl Compounds. Highly Regioselective<i>anti</i>-Markownikoff Type Oxidation of Allylic Alcohol Derivatives
  作者：Makoto Shimizu、Ryo Takeda、Isao Kuwajima

  DOI：10.1246/bcsj.54.3510

  日期：1981.11

  (C6H5Se)2–(C6H5SeO)2O system, oxoselenenylation reactions of C=C bonds have been examined with allylic and homoallylic alcohol derivatives, and substituted cyclohexenes, and allyl t-butyldimethylsilyl ethers are found to undergo regioselective conversion into β-siloxy α-phenylseleno carbonyl compounds in high yields.

  通过使用 (C6H5Se)2–t-BuOOH 或 (C6H5Se)2–(C6H5SeO)2O 系统，C=C 键的氧代硒烯基化反应已经用烯丙醇和高烯丙醇衍生物、取代的环己烯和烯丙基叔丁基二甲基甲硅烷基醚进行了研究发现以高产率进行区域选择性转化为 β-甲硅烷氧基 α-苯基硒羰基化合物。
• Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrin catalysts
  申请人：Che Chi-Ming

  公开号：US20050209470A1

  公开（公告）日：2005-09-22

  Diastereoselective epoxidation of allylically substituted alkenes using metalloporphyrins as catalyst provides high trans-selectivities (i.e., trans-:cis-epoxide ratio). A diversity of cycloalkenes bearing different allylic substituents are shown to be efficiently epoxidized to afford the corresponding trans-epoxides with excellent trans-selectivities (up to >98%) and good yields (up to 99%). Acyclic allylic alkenes bearing different allylic substituents are efficiently epoxidized to afford the corresponding erythro-epoxides with good erythro-selectivities. The metalloporphyrin-catalyzed reactions exhibit up to 20 times higher trans-selectivities than the conventional method using m-chloroperoxybenzoic acid as oxidant.

  使用金属卟啉作为催化剂的烯丙基取代烯烃的非对映选择性环氧化反应提供高选择性（即反式：顺式环氧化物比）。显示出带有不同烯丙基取代基的多样环烯烃能够有效地环氧化，产生相应的反式环氧化物，具有优异的反式选择性（高达>98%）和良好的产率（高达99%）。带有不同烯丙基取代基的无环烯丙基烯烃能够有效地环氧化，产生相应的顺式环氧化物，具有良好的顺式选择性。金属卟啉催化的反应显示出比使用m-氯过氧苯甲酸作为氧化剂的传统方法高达20倍的反式选择性。
• Highly Diastereoselective Epoxidation of Allyl-Substituted Cycloalkenes Catalyzed by Metalloporphyrins
  作者：Wing-Kei Chan、Peng Liu、Wing-Yiu Yu、Man-Kin Wong、Chi-Ming Che

  DOI：10.1021/ol0496475

  日期：2004.5.1

  Highly diastereoselective epoxidations of allyl-substituted cycloalkenes including allylic alcohols, esters, and amines using sterically bulky metalloporphyrins [Mn(TDCPP)Cl] (1) and [Ru(TDCPP)CO] (2) as catalysts have been achieved. The "1 + H(2)O(2)" and "2 + 2,6-Cl(2)pyNO" protocols afforded trans-epoxides selectively in good yields (up to 99%) with up to >99:1 trans-selectivity.

  使用空间庞大的金属卟啉[Mn（TDCPP）Cl]（1）和[Ru（TDCPP）CO]（2）作为催化剂，实现了烯丙基取代的环烯烃（包括烯丙醇，酯和胺）的高度非对映选择性环氧化。“ 1 + H（2）O（2）”和“ 2 + 2,6-Cl（2）pyNO”协议以良好的收率（高达99％）选择性地提供反式环氧化物，反式> 99：1 -选择性。
• Diastereoselective Diboration of Cyclic Alkenes: Application to the Synthesis of Aristeromycin
  作者：Alex J. Vendola、Christophe Allais、Anne-Marie R. Dechert-Schmitt、James T. Lee、Robert A. Singer、James P. Morken

  DOI：10.1021/acs.orglett.1c00353

  日期：2021.4.16

  The Pt-catalyzed diboration of cyclic alkenes is extended to unsaturated heterocycles and bicyclic compounds and can be accomplished in a diastereoselective fashion. The optimal procedures, substrate scope, and diastereoselectivity were investigated, and examples employing both homogeneous and heterogeneous catalysis were examined. Lastly, application to the construction of the nucleoside analog (±)-aristeromycin

  Pt催化的环烯烃的硼酸酯化反应扩展到不饱和杂环和双环化合物，并且可以以非对映选择性的方式完成。研究了最佳方法，底物范围和非对映选择性，并研究了采用均相和非均相催化的实例。最后，将其应用于核苷类似物（±）-阿霉素的构建。