3-(((tert-butyldimethylsilyl)oxy)methyl)cyclopent-2-en-1-one | 140840-85-3

• 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: 3-(((tert-butyldimethylsilyl)oxy)methyl)cyclopent-2-en-1-one
• 英文别名: 3-[[Tert-butyl(dimethyl)silyl]oxymethyl]cyclopent-2-en-1-one
• CAS: 140840-85-3
• 化学式: C₁₂H₂₂O₂Si
• 分子量: 226.391
• InChiKey: LBJZNDKLHUKXBU-UHFFFAOYSA-N

物化性质

• 熔点：
  65-67 °C
• 沸点：
  261.9±29.0 °C(Predicted)
• 密度：
  0.948±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(((tert-butyldimethylsilyl)oxy)methyl)cyclopent-2-en-1-one 在 甲醇 、 4-二甲氨基吡啶 、 bis{rhodium[3,3'-(1,3-phenylene)bis(2,2-dimethylpropanoic acid)]} 、 碘苯二乙酸 、 水 、 sodium hexamethyldisilazane 、 magnesium oxide 、 potassium carbonate 、 (±)-2,2 '-二(二-对甲苯基膦)-1,1 '-联萘 、 三乙胺 、 copper(l) chloride 、 sodium t-butanolate 作用下， 以 四氢呋喃 、 二氯甲烷 、 苯 为溶剂， 反应 99.25h， 生成 tert-Butyl [(1R,3S)-1-(hydroxymethyl)-3-{1-[(4-methylphenyl)sulfonyl]-1H-pyrrol-2-yl}cyclopentyl] carbamate
  参考文献：
  名称：

  Synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one as a key intermediate of sphingosine 1-phosphate-1 receptor agonists

  摘要：

  Herein we report the asymmetric synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one (S)-3 as a practical chiral synthon for a wide range of pharmaceutical and/or natural products, using Lipshutz's asymmetric copper-catalyzed conjugate reduction. This method makes it feasible to prepare a conformationally constrained cyclopentane analogue 12, which is one of the key intermediates for the synthesis of novel sphingosine 1-phosphate-1 receptor agonists. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.02.015
• 作为产物：
  描述：

  3-(benzenesulfonyl)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclopentan-1-one 在 三乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 以50.7 g的产率得到3-(((tert-butyldimethylsilyl)oxy)methyl)cyclopent-2-en-1-one
  参考文献：
  名称：

  Synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one as a key intermediate of sphingosine 1-phosphate-1 receptor agonists

  摘要：

  Herein we report the asymmetric synthesis of (3S)-(tert-butyldimethylsilyloxy)methylcyclopentan-1-one (S)-3 as a practical chiral synthon for a wide range of pharmaceutical and/or natural products, using Lipshutz's asymmetric copper-catalyzed conjugate reduction. This method makes it feasible to prepare a conformationally constrained cyclopentane analogue 12, which is one of the key intermediates for the synthesis of novel sphingosine 1-phosphate-1 receptor agonists. (C) 2013 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2013.02.015

文献信息

• Expanding the Scope of the Gold(I)-Catalyzed Rautenstrauch Rearrangement: Protic Additives
  作者：Cédric Bürki、Andrew Whyte、Sebastian Arndt、A. Stephen K. Hashmi、Mark Lautens

  DOI：10.1021/acs.orglett.6b02505

  日期：2016.10.7

  The synthesis of substituted 2-cyclopentenones using a commercially available gold(I) catalyst is described under flexible reaction conditions. During the course of our investigations, we discovered that using a proton source as an additive is required to obtain the desired substituted cyclopentenones in good yields.

  在柔性反应条件下描述了使用可商购的金（I）催化剂合成取代的2-环戊烯酮。在我们的研究过程中，我们发现需要使用质子源作为添加剂才能以高收率获得所需的取代的环戊烯酮。
• Rearrangement of 1-(1-Alkynyl)cyclopropanols to 2-Cyclopentenones via Their Hexacarbonyldicobalt Complexes. A New Use of Alkyne−Co₂(CO)₆ Complexes in Organic Synthesis
  作者：Nobuharu Iwasawa、Takeshi Matsuo、Mari Iwamoto、Taketo Ikeno

  DOI：10.1021/ja9734004

  日期：1998.4.1

  protective group of the substrates. This rearrangement was successfully applied to cyclopentenone annulation reactions onto cycloalkenes. An efficient synthesis of alkynyl-substituted bicyclo[n.1.0]alkanol derivatives from the corresponding cycloalkenes according to Danheiser's protocol was developed, and bicyclic cyclopentenones were obtained in moderate to good yield by applying to these the cobalt-mediated

  1-(1-炔基) 环丙醇向 2-环戊烯-1-酮的新重排是在其炔基部分与八羰基二钴 (Co2(CO8)) 络合后进行的。1-(1-炔基) 环丙醇在其炔烃末端具有广泛的取代基，以良好的产率重排为相应的 3-取代的 2-环戊烯-1-酮。In case of the reactions of 1-alkynylcyclopropanols with an alkyl substituent on the cyclopropane ring, either 4-substituted or 5-substituted 2-cyclopenten-1-ones could be selectively obtained by appropriate choice of stereochemistry and protective group of the substrates. 这种重排成功地应用于环戊烯酮环化成环烯烃的反应。根据
• A Novel Rearrangement of 1-Alkynylcyclopropanol to 2-Cyclopenten-1-one via Dicobalt Hexacarbonyl Complex
  作者：Nobuharu Iwasawa

  DOI：10.1246/cl.1992.473

  日期：1992.3

  Various 1-alkynylcyclopropanols are found to be converted to 3-substituted 2-cyclopenten-1-ones in good yields by heating their dicobalt hexacarbonyl complexes in refluxing tetrahydrofuran or dimethoxyethane.

  在回流的四氢呋喃或二甲氧基乙烷中加热二钴六羰基络合物，可将各种 1-炔基环丙醇转化为 3-取代的 2-环戊烯-1-酮，产量很高。
• Rearrangement of 1-Alkynylcyclopropanol to 3-Substituted 2-Cyclopentenone Promoted by a Catalytic Amount of Octacarbonyldicobalt-Triphenylphosphite
  作者：Nobuharu Iwasawa、Takeshi Matsuo

  DOI：10.1246/cl.1993.997

  日期：1993.6

  The rearrangement of 1-(1-alkynyl)cyclopropanols is catalyzed efficiently by the combined use of octacarbonyldicobalt and triphenylphosphite to give 3-substituted 2-cyclopentenones in high yields.

  联合使用八羰基二钴和亚磷酸三苯酯可高效催化 1-(1-炔基)环丙醇的重排反应，从而以高产率得到 3-取代的 2-环戊烯酮。
• Stable 5-Substituted Cyclopentadienes for the Diels-Alder Cycloaddition and their Application to the Synthesis of Palau'amine
  作者：Jonathan Hudon、Timothy A. Cernak、James A. Ashenhurst、James L. Gleason

  DOI：10.1002/anie.200803344

  日期：2008.11.3