1-trimethylsilyl-(3S,4S)-pent-1-yne-3,4-diol | 116223-15-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-trimethylsilyl-(3S,4S)-pent-1-yne-3,4-diol
• 英文别名: (3S,4S)-1-Trimethylsilyl-4-pentyne-3,4-diol；(3S,4S)-1-trimethylsilyl-1-pentyne-3,4-diol；(2S,3S)-5-trimethylsilylpent-4-yne-2,3-diol
• CAS: 116223-15-5
• 化学式: C₈H₁₆O₂Si
• 分子量: 172.299
• InChiKey: AQAYEIYXNAPNCQ-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.61
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  40.5
• 氢给体数：
  2
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-trimethylsilyl-(3S,4S)-pent-1-yne-3,4-diol 在 copper(l) iodide 、 cyclopentadienylW(carbonyl)3 、 N,N-二异丙基乙胺 作用下， 以 二乙胺 为溶剂， 生成 (3E,4S,5S)-4-(methoxymethoxy)-5-methyl-3-tetradec-2-ynylideneoxolan-2-one
  参考文献：
  名称：

  Asymmetric synthesis of (−)-epi-blastmycinone and (2R,3S,4S)-3-hydroxy-4-methyl-2-(1′-n-tetradecyl)-butanolide via a tungsten-mediated cyclization reaction

  摘要：

  Enantiocontrolled syntheses of the natural lactones 1 and 2 were achieved based on a tungsten-mediated cyclization. The whole syntheses comprise of six or seven steps from readily available 1-trimethylsilyl-pent-1-yne; the overall yields are 25 and 28% for 1 and 2, respectively. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00189-7
• 作为产物：
  描述：

  (E)-trimethyl(pent-3-en-1-yn-1-yl)silane 在 AD-mix-α 、 甲基磺酰胺 作用下， 以71%的产率得到1-trimethylsilyl-(3S,4S)-pent-1-yne-3,4-diol
  参考文献：
  名称：

  Asymmetric synthesis of (−)-epi-blastmycinone and (2R,3S,4S)-3-hydroxy-4-methyl-2-(1′-n-tetradecyl)-butanolide via a tungsten-mediated cyclization reaction

  摘要：

  Enantiocontrolled syntheses of the natural lactones 1 and 2 were achieved based on a tungsten-mediated cyclization. The whole syntheses comprise of six or seven steps from readily available 1-trimethylsilyl-pent-1-yne; the overall yields are 25 and 28% for 1 and 2, respectively. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)00189-7

文献信息

• Total Synthesis of (+)-Blastmycinone, (−)-Litsenolide C₁, and Related Natural Trisubstituted Lactones via Alkynyltungsten Compounds
  作者：Ming-Jung Chen、Ching-Yu Lo、Chih-Chien Chin、Rai-Shung Liu

  DOI：10.1021/jo0002487

  日期：2000.10.1

  A general method for total synthesis of natural trisubstituted gamma-lactones is developed on the basis of the chemistry of alkynyltungsten compounds. The key step in this approach involves the cycloalkenation of tungsten-eta1-(3R,4S)-pent-1-yne-3,4-diol with aldehydes to give tungsten-oxacarbenium salts, further leading to 3-alkylidene-4-hydroxy-5-methyl-gamma-lactones upon demetalation. This synthetic

  根据炔烃钨化合物的化学性质，开发了一种全合成天然三取代γ-内酯的通用方法。该方法的关键步骤涉及将钨-eta1-（3R，4S）-戊-1-炔-3,4-二醇与醛进行环烯化反应生成钨-氧杂碳鎓盐，进一步导致3-亚烷基-4-羟基脱金属时的-5-甲基-γ-内酯。对于炔醛和钨-eta1-（3R，4S）-戊-1-炔-3,4-二醇的MOM衍生物，该合成序列进展顺利。将所得丁内酯产物转化为天然三取代丁内酯，包括（+）-blastmycinone，（+）-blastmycinactactol，（+）-antimycinone，NFX-2和（+）-isodihydromahubanolideA。通过基于（R ）-乳酸乙酯，可以通过几个步骤制备天然（-）-litsenolide C1。
• Selective Synthesis of Chiral Dioxabicyclo[4.4.0]decane and Dioxabicyclo[5.3.0]decane from 3,4-Bisallyloxy-but-1-yne Derivatives via Ruthenium-Catalyzed En-yn-ene Metathesis
  作者：Chang-Jung Wu、Reniguntala J. Madhushaw、Rai-Shung Liu

  DOI：10.1021/jo0301548

  日期：2003.10.1

  Grubbs catalyst Cl2(PCy3)2Ru=CHPh (3 mol %) preferably gave chiral dioxabicyclo[4.4.0]decane (yields > 55%) in addition to dioxabicyclo[5.3.0]decane in minor proportions. On substitution of the 4-allyloxy group of these substrates with a 4-but-2-enyloxy group, the metathesis reactions produced only dioxabicyclo[5.3.0]decane in the presence of Grubbs ruthenium-imidazolidene carbene catalyst.

  我们制备了一系列具有顺式和反式构型的手性3,4-双烯丙氧基-丁-1-炔。除了少量的二氧杂双环[5.3.0]癸烷外，用Grubbs催化剂Cl 2（PCy 3）2 Ru ＝ CHPh（3mol％）处理这些底物优选得到手性的二氧杂双环[4.4.0]癸烷（收率＞ 55％）。在这些底物的4-烯丙氧基被4-丁-2-烯氧基取代后，在Grubbs钌-咪唑啉卡宾催化剂的存在下，复分解反应仅生成二氧杂双环[5.3.0]癸烷。
• Guanti, Giuseppe; Banfi, Luca; Narisano, Enrica, Gazzetta Chimica Italiana, 1987, vol. 117, # 11, p. 681 - 688
  作者：Guanti, Giuseppe、Banfi, Luca、Narisano, Enrica

  DOI：——

  日期：——
• Chen; Lo; Liu, Synlett, 2000, # 8, p. 1205 - 1207
  作者：Chen、Lo、Liu

  DOI：——

  日期：——
• Stereoselective synthesis of syn-1,3-diols
  作者：Peter Mohr

  DOI：10.1016/s0040-4039(00)79685-7

  日期：1991.5

  beta-Hydroxyalkynones 1, readily available from the corresponding beta-hydroxyesters, are reduced by DIBAL-H in THF at -78-degrees with good selectivity to syn-diols 2.