(Z)-5<(tert-butyldimethylsilyl)oxy>3,4-epoxy-3-methyl-1-pentyne

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (Z)-5<(tert-butyldimethylsilyl)oxy>3,4-epoxy-3-methyl-1-pentyne
• 英文别名: cis-1-(tert-butyldimethylsilyloxy)-2,3-epoxy-3-methylpent-4-yne；cis-1-(t-butyldimethylsilyloxy)-3-methyl-2,3-epoxypent-4-yne；tert-butyl-[[(2R,3S)-3-ethynyl-3-methyloxiran-2-yl]methoxy]-dimethylsilane
• 化学式: C₁₂H₂₂O₂Si
• 分子量: 226.391
• InChiKey: XZPKWJFCZOHCDB-PWSUYJOCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  21.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-5<(tert-butyldimethylsilyl)oxy>3,4-epoxy-3-methyl-1-pentyne 在 草酰氯 、 copper(I) bromide dimethylsulfide complex 、 二甲基亚砜 、 三乙胺 作用下， 反应 1.67h， 生成 1-<(tert-butyldimethylsilyl)oxy>-3-methyl-3,4-undecadien-2-one
  参考文献：
  名称：

  Synthesis of furans by base-catalyzed cyclization-isomerization of .beta.- and .gamma.-alkynyl allylic alcohols

  摘要：

  Beta- and gamma-alkylyl allylic alcohols 3, 13, 26, available through Pd-mediated coupling of appropriate vinylic halides and terminal alkynes, cyclize and subsequently isomerize to furans 4, 17, and 32 upon treatment with KO-t-Bu in t-BuOH-THF at 25-60-degrees-C. The methodology has been used to prepare 2,3-, 2,4-, and 2,3,5-substituted furans. Reactions in t-BuOD as cosolvent lead to deuterium incorporation consistent with concurrent pathways in which direct 5-exo-dig or 5-endo-dig cyclization of the alkynyl allylic alcohol competes with prior isomerization to an allene intermediate which subsequently cyclizes by 5-exo- or 5-endo-dig pathways.

  DOI：

  10.1021/jo00064a038
• 作为产物：
  描述：

  (Z)-3-甲基戊-2-烯-4-炔-1-醇 在 4-二甲氨基吡啶 、 disodium hydrogenphosphate 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 6.0h， 生成 (Z)-5<(tert-butyldimethylsilyl)oxy>3,4-epoxy-3-methyl-1-pentyne
  参考文献：
  名称：

  Synthesis of furans by base-catalyzed cyclization-isomerization of .beta.- and .gamma.-alkynyl allylic alcohols

  摘要：

  Beta- and gamma-alkylyl allylic alcohols 3, 13, 26, available through Pd-mediated coupling of appropriate vinylic halides and terminal alkynes, cyclize and subsequently isomerize to furans 4, 17, and 32 upon treatment with KO-t-Bu in t-BuOH-THF at 25-60-degrees-C. The methodology has been used to prepare 2,3-, 2,4-, and 2,3,5-substituted furans. Reactions in t-BuOD as cosolvent lead to deuterium incorporation consistent with concurrent pathways in which direct 5-exo-dig or 5-endo-dig cyclization of the alkynyl allylic alcohol competes with prior isomerization to an allene intermediate which subsequently cyclizes by 5-exo- or 5-endo-dig pathways.

  DOI：

  10.1021/jo00064a038

文献信息

• From Amino Acids To Dihydrofurans: Functionalized Allenes in Modern Organic Synthesis
  作者：Norbert Krause、Anja Hoffmann-Röder、Johannes Canisius

  DOI：10.1055/s-2002-33707

  日期：——

  In this account, recent accomplishments in the field of target-oriented synthesis involving allenes are summarized. Allenic α-amino acid derivatives 9, which are of interest as possible vitamin B 6 decarboxylase inhibitors, were prepared by 1,6-addition of the cyano-Gilman reagent t-Bu 2 CuLi-LiCN to 2-amino-substituted enynoates 8. and selective deprotection at either the amino or the ester group

  本文总结了最近在涉及丙二烯的靶向合成领域取得的成就。通过将氰基-吉尔曼试剂 t-Bu 2 CuLi-LiCN 与 2-氨基取代的烯醇酸酯 8 进行 1,6-加成，制备了可能作为维生素 B 6 脱羧酶抑制剂的艾伦族 α-氨基酸衍生物 9。并实现了氨基或酯基的选择性脱保护。2,5-二氢呋喃18由相应的α-羟基丙二烯环化得到；对于这一步，开发了新的方法（用氯化氢气体或酸性离子交换树脂处理；金（III）-氯化物催化）。2-羟基-3,4-二烯酸 14 是通过用二甲基二环氧乙烷 (DMDO) 对由 3,4-二烯酸 12 形成的钛烯醇化物进行非对映选择性氧化获得的，
• Rapid Generation of Molecular Complexity: Synthesis of α-Hydroxyallenes Using Functionalized Grignard Reagents
  作者：Norbert Krause、Carl Deutsch、Anja Hoffmann-Röder、Axel Domke

  DOI：10.1055/s-2007-970768

  日期：2007.3

  reagents in the copper-mediated S N 2′ substitution of propargylic oxiranes leads to structurally complex α-hydroxyallenes, usually with high yield and diastereoselectivity. Further transformations, such as gold-catalyzed cycloisomerization to 2,5-dihydrofurans and palladium-catalyzed coupling reactions, demonstrate the high potential of these compounds for the rapid generation of molecular complexity

  在铜介导的炔丙基环氧乙烷的 SN 2' 取代中使用官能化的芳基-格氏试剂导致结构复杂的 α-羟基丙二烯，通常具有高产率和非对映选择性。进一步的转化，例如金催化的环异构化为 2,5-二氢呋喃和钯催化的偶联反应，证明了这些化合物在快速生成分子复杂性方面的巨大潜力。
• Stereoselective Synthesis of<i>syn</i>-Configured α-Allenols by Rhodium-Catalyzed Reaction of Alkynyl Oxiranes with Arylboronic Acids
  作者：Tomoya Miura、Masahiko Shimada、Paula de Mendoza、Carl Deutsch、Norbert Krause、Masahiro Murakami

  DOI：10.1021/jo900987w

  日期：2009.8.21

  A rhodium-catalyzed reaction of alkynyl oxiranes with arylboronic acids affords syn-configured α-allenols with high diastereoselectivity. The reaction is initiated by addition of an arylrhodium(I) species onto the alkyne moiety of the alkynyl oxirane. The resulting alkenylrhodium(I) intermediate undergoes β-oxygen elimination to open the oxirane ring in a syn-selective fashion. Protonolysis of the

  炔基肟基与芳基硼酸的铑催化反应提供了具有高非对映选择性的顺式构型α-烯醇。通过将芳基铑（I）物质加到炔基环氧乙烷的炔基部分上来引发反应。所得的烯基铑（I）中间体经历β-氧消除，以顺选择方式打开环氧乙烷环。用芳基硼酸对醇铑（I）进行质子分解会释放出相应的α-烯醇和硼酸铑（I），后者会经过β-芳基消除反应，从而再生出芳基铑（I）物种。该方法的实用性通过在（±）-Boivinianin B的简明合成中的应用得到证明。
• Synthesis of Bicyclic Ethers by a Gold/Palladium/Gold-Catalyzed Cyclization/Cross Coupling Sequence
  作者：Birgit Gockel、Norbert Krause

  DOI：10.1002/ejoc.200901010

  日期：2010.1

  The stereoselective gold-catalyzed 6-endo cyclization of various β-hydroxyallenes in the presence of N-iodosuccinimide affords iodinated dihydropyrans in good yield. Subsequent functionalization by palladium-catalyzed cross coupling opens an access to α-hydroxyallenes that are converted in a second gold-catalyzed cyclization into furopyrans which occur in various natural products.

  在 N-碘代琥珀酰亚胺存在下，各种 β-羟基丙二烯的立体选择性金催化 6-内环化以良好的收率提供碘化二氢吡喃。随后通过钯催化的交叉偶联进行的功能化打开了获得 α-羟基丙二烯的途径，这些α-羟基丙二烯在第二次金催化的环化中转化为呋喃吡喃，呋喃吡喃存在于各种天然产物中。
• Synthesis of Highly Functionalized Propargylic Alcohols: Direct Addition of Epoxy Acetylides to Aldehydes and Ketones
  作者：Anja Hoffmann-Röder、Norbert Krause

  DOI：10.1002/1522-2675(200210)85:10<3176::aid-hlca3176>3.0.co;2-7

  日期：2002.10

  Direct nucleophilic addition of terminal alkynes comprising an epoxy group to aldehydes and ketones is reported with BuLi or lithium diisopropylamide for the generation of the corresponding lithium acetylides. This alkynylation reaction tolerates a wide variety of different functional groups (e.g.. alcohols. silyl ethers. halides, double bonds) in the carbonyl compound, as well as in the acetylenic nucleophile, and furnishes highly functionalized propargylic alcohols in good-to-excel lent yields. The method is particularly useful for the regioselective introduction of an epoxide function into multiply unsaturated target molecules.