6-((1,1-dimethylethyl)diphenylsilyloxy)hexanoic acid methyl ester | 146830-59-3

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 6-((1,1-dimethylethyl)diphenylsilyloxy)hexanoic acid methyl ester
• 英文别名: 6-(tert-butyldiphenylsilanyloxy)hexanoic acid methyl ester；methyl 6-(tert-butyldiphenylsilyloxy)hexanoate；Hexanoic acid, 6-[[(1,1-dimethylethyl)diphenylsilyl]oxy]-, methyl ester；methyl 6-[tert-butyl(diphenyl)silyl]oxyhexanoate
• CAS: 146830-59-3
• 化学式: C₂₃H₃₂O₃Si
• 分子量: 384.591
• InChiKey: OZZRRRPTSPJZNJ-UHFFFAOYSA-N

物化性质

• 沸点：
  428.4±37.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  27
• 可旋转键数：
  11
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  6-((1,1-dimethylethyl)diphenylsilyloxy)hexanoic acid methyl ester 在 1-氯乙基氯甲酸酯 作用下， 以 甲醇 为溶剂， 反应 3.5h， 以93%的产率得到6-羟基己酸甲酯
  参考文献：
  名称：

  Efficient chemoselective deprotection of silyl ethers using catalytic 1-chloroethyl chloroformate in methanol

  摘要：

  Fast and chemoselective desilylation of silyl-protected alcohols was achieved using a catalytic amount of 1-chloroethyl chloroformate in methanol. With a minimal amount of 1-chloroethyl chloroformate as the source for anhydrous HCl, extremely efficient cleavage of silyl ethers of primary and secondary alcohols was accomplished, and chemoselective deprotection of one silyl ether in the presence of another silyl or other acid-labile group was possible through controlling the amount of the chloroformate and reaction time. (c) 2005 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2005.10.043
• 作为产物：
  描述：

  6-己内酯 在 咪唑 作用下， 以 甲醇 、 N,N-二甲基甲酰胺 为溶剂， 反应 24.0h， 生成 6-((1,1-dimethylethyl)diphenylsilyloxy)hexanoic acid methyl ester
  参考文献：
  名称：

  Total synthesis of natural gingerols, the three active principles of ginger

  摘要：

  Natural gingerols, (+)(S)[6]-, (+)(S)[8]-, and (+)(S)[10]-gingerols, the three active principles of ginger, have been prepared from a common optically active intermediate 9 which was readily made by asymmetric synthesis from a chiral beta-keto sulfoxide 5.

  DOI：

  10.1021/jo00060a038

文献信息

• Copper-Catalyzed and Indium-Mediated Methoxycarbonylation of Unactivated Alkyl Iodides with Balloon CO
  作者：Yanchi Chen、Lei Su、Hegui Gong

  DOI：10.1021/acs.orglett.9b01573

  日期：2019.6.21

  This work emphasizes the synthesis of alkyl esters via Cu-catalyzed and In-mediated alkoxycarbonylation of unactivated alkyl iodides in the presence of In or InI. The reactions were suitable for the preparation of primary, secondary, and even tertiary alkyl esters, representing an exceptionally rare example for the creation of quaternary carbon centers upon formation of esters. The preliminary mechanistic

  这项工作强调在In或InI的存在下，通过Cu催化和In介导的未活化烷基碘的烷氧基羰基化来合成烷基酯。该反应适合于伯，仲，甚至叔烷基酯的制备，代表了在形成酯时生成季碳中心的极为罕见的例子。初步的机理研究表明，涉及烷基自由基，而Cu / In / CO在羰基化事件中起着协同作用。
• Catalytic Asymmetric Synthesis of Macrocyclic (<i>E</i>)-Allylic Alcohols from ω-Alkynals via Intramolecular 1-Alkenylzinc/Aldehyde Additions
  作者：Wolfgang Oppolzer、Rumen N. Radinov、Emad El-Sayed

  DOI：10.1021/jo000463n

  日期：2001.7.1

  The omega-alkynals yielded macrocyclic (S)-allylic alcohols in a one-pot reaction sequence involving alkyne monohydroboration, boron to zinc transmetalation, and ((+)-DAIB)-catalyzed enantioselective intramolecular ring closure to the aldehyde function. A general study of this macrocyclization methodology is presented with respect to ligand type, size, and nature of the formed rings.

  ω-炔烃在一锅反应序列中生成大环（S）-烯丙基醇，涉及炔烃单氢硼化，硼到锌的金属转移和（（+）-DAIB）催化的对醛官能团的对映选择性分子内闭环。有关配体类型，大小和形成环的性质，对这种大环化方法进行了一般研究。
• Stereoselective synthesis of the head group of archaeal phospholipid PGP-Me to investigate bacteriorhodopsin–lipid interactions
  作者：Jin Cui、Satoshi Kawatake、Yuichi Umegawa、Sébastien Lethu、Masaki Yamagami、Shigeru Matsuoka、Fuminori Sato、Nobuaki Matsumori、Michio Murata

  DOI：10.1039/c5ob01252j

  日期：——

  Phosphatidylglycerophosphate methyl ester (PGP-Me), a major constituent of the archaeal purple membrane, is essential for the proper proton-pump activity of bacteriorhodopsin (bR).

  磷脂甘油磷酸甲酯（PGP-Me）是古菌紫膜的主要成分，对于细菌紫质蛋白（bR）的正确质子泵活性至关重要。
• Novel Oxepane Formation by TiCl4-Catalyzed Nucleophilic Cleavage of 1-Alkoxymethyl-6,8-dioxabicyclo[3.2.1]octanes
  作者：Kenshu Fujiwara、Arika Amano、Tetsuo Tokiwano、Akio Murai

  DOI：10.1016/s0040-4020(00)00009-0

  日期：2000.2

  Introduction of an alkoxymethyl group at the C1 position in the 6,8-dioxabicyclo[3.2.1]octane system enabled novel formation of oxepane compounds in TiCl4-catalyzed acetal cleavage reactions.

  在6,8-二氧杂双环[3.2.1]辛烷系统的C1位置引入烷氧基甲基可以在TiCl 4催化的缩醛裂解反应中新形成环氧丙烷化合物。
• Construction of the Key Amino Alcohol Moiety of the Cinchona Alkaloids
  作者：Yuichi Kobayashi、Yuuya Motoyama

  DOI：10.1055/s-2006-950435

  日期：2006.9

  An N-Teoc [CO2(CH2)2TMS] protected form of the amino alcohol moiety found in the cinchona alkaloids was constructed by Curtius rearrangement followed by reaction of the isocyanate ­intermediate with TMS(CH2)2OH in one pot. Deprotection of the N-Teoc protective group and subsequent piperidine ring formation were easily accomplished with CsF in DMF at 110 °C in one pot to afford model compounds of the alkaloids.

  通过 Curtius 重排，然后将异氰酸酯中间体与 TMS(CH2)2OH 反应，在一个反应釜中构建了金鸡纳生物碱中氨基醇的 N-Teoc [CO2(CH2)2TMS] 保护形式。N-Teoc 保护基团的脱保护和随后的哌啶环形成可在 DMF 中用 CsF 在 110 ℃ 下一次反应轻松完成，从而得到生物碱的模型化合物。