1-(t-butyldimethylsilyloxy)-3-methylundeca-3,4-dien-2-ol | 148457-16-3

• 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-(t-butyldimethylsilyloxy)-3-methylundeca-3,4-dien-2-ol
• 英文别名: 1-<(tert-butyldimethylsilyl)oxy>-3-methyl-3,4-undecadien-2-ol；1-(tert-butyldimethylsilyloxy)-3-methylundeca-3,4-dien-2-ol；1-[tert-butyl(dimethyl)silyl]oxy-3-methylundeca-3,4-dien-2-ol
• CAS: 148457-16-3
• 化学式: C₁₈H₃₆O₂Si
• 分子量: 312.568
• InChiKey: VNAKDZYLSFVKHY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.44
• 重原子数：
  21.0
• 可旋转键数：
  9.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  29.46
• 氢给体数：
  1.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-(t-butyldimethylsilyloxy)-3-methylundeca-3,4-dien-2-ol 在 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 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 、 copper(I) bromide dimethylsulfide complex 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 7.42h， 生成 1-(t-butyldimethylsilyloxy)-3-methylundeca-3,4-dien-2-ol
  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，
• Gold-Catalyzed Cycloisomerization of α-Aminoallenes to 3-Pyrrolines –Optimization and Mechanistic Studies
  作者：Nobuyoshi Morita、Norbert Krause

  DOI：10.1002/ejoc.200600438

  日期：2006.10

  epimerization of the allene in the presence of the gold precatalyst. The low reactivity of the intramolecular hydroamination of unprotected α-aminoallenes with AuCl3 was improved by use of gold(I) halides as the precatalyst. Mechanistic studies suggest that a gold(I) compound (formed by oxidation of the aminoallene) is the catalytically active species even if the reaction is started with a gold(III) precatalyst

  各种 α-氨基丙二烯的金催化环异构化以良好到高的化学产率提供相应的 3-吡咯啉，并且 - 如果氨基未受保护 - 具有完整的轴到中心手性转移。在 N 保护底物的情况下观察到手性转移水平降低，这可能是在金预催化剂存在下丙二烯部分差向异构化的结果。通过使用金 (I) 卤化物作为预催化剂，未保护的 α-氨基丙二烯与 AuCl3 的分子内加氢胺化的低反应性得到了改善。机理研究表明，即使反应以金 (III) 预催化剂开始，金 (I) 化合物（通过氨基丙二烯氧化形成）也是催化活性物质。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Gold(III) Chloride Catalyzed Cyclization of α-Hydroxyallenes to 2,5-Dihydrofurans
  作者：Anja Hoffmann-Röder、Norbert Krause

  DOI：10.1021/ol016205+

  日期：2001.8.9

  corresponding 2,5-dihydrofurans 2 by using 5-10 mol % of gold(III) chloride as catalyst. This mild and efficient cyclization method can be applied to alkyl- and alkenyl-substituted allenes at room temperature, furnishing tri- and tetrasubstituted dihydrofurans in good to excellent chemical yields and with complete axis to center chirality transfer.

  [反应：见正文]通过使用5-10 mol％的氯化金（III）催化剂，可以将官能化的α-羟基丙烯1平稳地转化为相应的2,5-二氢呋喃2。这种温和而有效的环化方法可在室温下应用于烷基和烯基取代的烯，以良好的化学收率和良好的轴向中心手性转移提供三和四取代的二氢呋喃。
• Marshall James A., DuBay William J., J. Org. Chem., 58 (1993) N 12, S 3435-3443
  作者：Marshall James A., DuBay William J.

  DOI：——

  日期：——