(S)-4-trimethylsilyl-3-butyn-2-yl mesylate | 375395-74-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: (S)-4-trimethylsilyl-3-butyn-2-yl mesylate
• 英文别名: (S)-3-butyn-2-ol；[(2S)-4-trimethylsilylbut-3-yn-2-yl] methanesulfonate
• CAS: 375395-74-7
• 化学式: C₈H₁₆O₃SSi
• 分子量: 220.365
• InChiKey: WECIJDDZFSZGAQ-QMMMGPOBSA-N

物化性质

• 沸点：
  272.4±23.0 °C(Predicted)
• 密度：
  1.062±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.23
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  51.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S)-4-trimethylsilyl-3-butyn-2-yl mesylate 在 palladium diacetate 、 indium iodide 、 三乙胺 、 三苯基膦 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 二氯甲烷 为溶剂， 反应 0.25h， 生成 tert-butyl-[(2S,3S,4S)-2,4-dimethyl-1-phenylmethoxy-6-trimethylsilylhex-5-yn-3-yl]oxy-dimethylsilane
  参考文献：
  名称：

  Coupling of AlkynylTMS Derivatives with Vinylic Iodides. An Efficient Route to 1,3-Enynes and Dienes

  摘要：

  [GRAPHICS]CuCl-promoted coupling of alkynylTMS derivatives with vinyl iodides leads to 1,3-enynes in high yield. Enynes prepared! from homopropargylic alcohols undergo intramolecular hydrosilylation and subsequent silyl cleavage with TBAF to afford 1,3-dienes.

  DOI：

  10.1021/ol016899m
• 作为产物：
  描述：

  4-三甲基硅基-3-丁炔-2-酮 在 甲酸 、 三乙胺 、 (1S,2S)-(+)-N-对甲苯磺酰基-1,2-二苯基乙二胺 作用下， 以 二氯甲烷 为溶剂， 反应 1.0h， 生成 (R)-4-trimethylsilyl-3-butyn-2-yl mesylate 、 (S)-4-trimethylsilyl-3-butyn-2-yl mesylate
  参考文献：
  名称：

  Cyclopropane Compatibility with Oxidative Carbocation Formation: Total Synthesis of Clavosolide A

  摘要：

  Cyclopropane-substituted allylic ethers react with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone to form oxocarbenium ions with no competitive ring cleavage. This reaction can be used for the preparation of cyclopropane-substituted tetrahydropyrans. The protocol was used as a key step in the total synthesis of the sponge-derived macrolide clavosolide A.

  DOI：

  10.1021/ol302744t

文献信息

• A Pentenyl Dianion-Based Strategy for Convergent Synthesis of Ene-1,5-diols
  作者：Adilah B. Bahadoor、Alec Flyer、Glenn C. Micalizio

  DOI：10.1021/ja050039+

  日期：2005.3.1

  A convergent two-step process is described for the synthesis of ene-1,5-diols that provides for union of two carbonyl electrophiles via a formal pentenyl dianion equivalent.

  介绍了一种收敛的两步法，用于合成 ene-1,5-二醇，通过正式的戊烯基二阴离子等效物提供两个羰基亲电试剂的结合。
• Crotylation versus Propargylation:  Two Routes for the Synthesis of the C13−C18 Fragment of the Antibiotic Branimycin
  作者：Wolfgang Felzmann、Daniele Castagnolo、Daniela Rosenbeiger、Johann Mulzer

  DOI：10.1021/jo062502m

  日期：2007.3.1

  The C13−C18 fragment 3 of the novel antibiotic branimycin was prepared along two highly stereocontrolled routes. The first one uses a standard Roush crotylation protocol, whereas the second one proceeds via an allenyl silane propargylation with unexpected stereochemical consequences, which are discussed in detail.

  新型抗生素布雷尼霉素的C13-C18片段3沿两条高度立体控制的途径制备。第一个使用标准的Roush crotylation协议，而第二个通过烯丙基硅烷的炔丙基化进行，具有意想不到的立体化学后果，将对此进行详细讨论。
• Total Synthesis of Iejimalide B. An Application of the Shiina Macrolactonization
  作者：Dirk Schweitzer、John J. Kane、Daniel Strand、Peter McHenry、Martin Tenniswood、Paul Helquist

  DOI：10.1021/ol702129w

  日期：2007.10.1

  The potent anticancer compound iejimalide B (1) was prepared by a total synthesis through a strategy that features Julia olefinations, Wittig olefinations, a Carreira enantioselective alkynylation, a Heck reaction, a Marshall propargylation reaction, a Stille coupling, and a Shiina macrolactonization.

  有效的抗癌化合物iejimalide B（1）是通过全合成方法制得的，该策略的特征是朱莉娅烯化，维蒂希烯化，Carreira对映体选择性炔基化，Heck反应，马歇尔炔丙基化反应，Stille偶联和Shiina大内酯化。
• Lipase-Mediated Resolution of 4-TMS-3-butyn-2-ol and Use of the Mesylate Derivatives as a Precursor to a Highly Stereoselective Chiral Allenylindium Reagent
  作者：James A. Marshall、Harry R. Chobanian、Mathew M. Yanik

  DOI：10.1021/ol016605x

  日期：2001.10.1

  [GRAPHICS]An improved procedure for the resolution of 4-trimethylsilyl-3-butyn-2-ol has been developed. The mesylate derivatives of the resolved alcohols have been found to undergo highly enantio-, regio-, and diastereoselective additions to aldehydes, leading to homopropargylic alcohol adducts.
• Synthesis of the C6−C21 Segment of Amphidinolide E
  作者：James A. Marshall、Gregory Schaaf、Andrew Nolting

  DOI：10.1021/ol0523493

  日期：2005.11.1

  A convergent approach to a C6-C21 segment of the polyketide amphidinolide E has been developed through combination of three subunits by allenylindium bromide-aldehyde addition and Suzuki sp(2-)sp(3) coupling.