trans-^tbutyldimethylsiloxy-2-cyclopenten-4-ol | 61740-31-6

• 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: trans-^tbutyldimethylsiloxy-2-cyclopenten-4-ol
• 英文别名: trans-(1S,4S)-4-(tert-butyldimethylsiloxy)-2-cyclopenten-1-ol；(1R,3R)-1-(tert-butyl-dimethylsiloxy)-3-hydroxy-4-cyclopentene；(1S,4S)-4-t-butyldimethylsiloxy-2-cyclopenten-1-ol；4-((tert-butyldimethylsilyl)oxy)cyclopent-2-en-1-ol；(1S,4S)-4-[tert-butyl(dimethyl)silyl]oxycyclopent-2-en-1-ol
• CAS: 61740-31-6
• 化学式: C₁₁H₂₂O₂Si
• 分子量: 214.38
• InChiKey: VRSPJPYUHXNQHT-NXEZZACHSA-N

物化性质

• 沸点：
  245.9±40.0 °C(Predicted)
• 密度：
  0.94±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  trans-^tbutyldimethylsiloxy-2-cyclopenten-4-ol 在 palladium on activated charcoal 氢氧化钾 、 盐酸羟胺 、 四丁基氟化铵 、 氢气 、 sodium hydride 、 甲基磺酰氯 、 N,N-二异丙基乙胺 、 三苯基膦 、 lithium iodide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 130.0 ℃ 、101.33 kPa 条件下， 反应 83.75h， 生成 (1S,3R)-1-(9-adenenyl)-3-(N-hydroxycarbamoylmethyl)cyclopentane
  参考文献：
  名称：

  Metal Coordination-Based Inhibitors of Adenylyl Cyclase:  Novel Potent P-Site Antagonists

  摘要：

  The adenylyl cyclases (ACS) are a family of intracellular enzymes associated with signal transduction by virtue of their ability to convert ATP to cAMP. The catalytic mechanism of this transformation proceeds through initial binding of ATP to the so-called purine binding site (P-site) of the enzyme followed by metal-mediated cyclization with loss of pyrophosphate. Crystallographic analysis of ACs with known inhibitors reveals the presence of two metals in the active site. Presently, nine isoforms of adenylyl cyclase are known, and unique isoform combinations are expressed in a tissue-specific manner. The development of isoform-specific inhibitors of adenylyl cyclase may prove to be a useful strategy toward the design of unique signal transduction inhibitors. To develop novel AC inhibitors, we have chosen an approach to inhibitor design utilizing an adenine ring system joined to a metal-coordinating hydroxamic acid via various linkers. Previous work in our group has validated this approach and identified novel inhibitors that possess an adenine ring joined to a metal-coordinating hydroxamic acid through flexible acyclic linkers (Levy, D. E., et al. Bioorg. Med. Chem. Lett. 2002, 12, 30853088). Subsequent studies have focused on the introduction of conformational restrictions into the tether of the inhibitors with the goal of increasing potency (Levy, D. E., et al. Bioorg. Med. Chem. Lett. 2002, 12, 3089-3092). Building upon the favorable spatial positioning of the adenine and hydroxamate groups coupled with potentially favorable entropic factors, the unit joining the carbocycle to the hydroxamate was explored further and a stereochemical-based SAR was elucidated, leading to a new series of highly potent AC inhibitors.

  DOI：

  10.1021/jm0205604
• 作为产物：
  描述：

  Cis-3,5-二乙酰氧基-1-环戊烯 在 sodium azide 、 对硝基苯甲醇 、 偶氮二甲酸二异丙酯 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 trans-^tbutyldimethylsiloxy-2-cyclopenten-4-ol
  参考文献：
  名称：

  [EN] FUSED TRICYCLIC ETHER CARBAMATES AND THEIR USE
  [FR] ETHER CARBAMATES TRICYCLIQUES FUSIONNÉS ET LEUR UTILISATION

  摘要：

  公开号：

  WO2012031237A8

文献信息

• Catalysis‐Enabled Concise and Stereoselective Total Synthesis of the Tricyclic Prostaglandin D ₂ Metabolite Methyl Ester
  作者：Hunter S. Sims、Pedro Andrade Horn、Ryota Isshiki、Melissa Lim、Yan Xu、Robert H. Grubbs、Mingji Dai

  DOI：10.1002/anie.202115633

  日期：2022.1.26

  The clinically important tricyclic prostaglandin D2 metabolite (PGDM) methyl ester was synthesized in eight steps from a readily available known compound. The synthesis features Z-selective cross-metathesis to form the challenging Z β,γ-unsaturated ester, palladium-catalyzed carbonylative spirolactonization to build the oxaspirolactone moiety, and nickel-catalyzed Ueno–Stork-type dicarbofunctionalization

  临床上重要的三环前列腺素 D2 代谢物 （PGDM） 甲酯是从现成的已知化合物中分 8 个步骤合成的。该合成的特点是 Z 选择叉复分解形成具有挑战性的 Z β，γ-不饱和酯，钯催化的羰基化螺内酯化以构建氧代内酯部分，以及镍催化的 Ueno-Stork 型二碳功能化以形成两个关键的 C-C 键和立体中心。
• A general method for iterative cyclopentannulation: sequential use of Claisen rearrangement and radical enyne closure
  作者：Derrick L. J. Clive、Hartford W. Manning

  DOI：10.1039/c39930000666

  日期：——

  Cycloalkenyl acetylenes 4, which are easily prepared from allylic alcohols 1, undergo radical cyclization (4→5) on treatment with stannyl radicals; the products 5 are themselves convertible into allylic alcohols, so that the annulation sequence can be repeated.

  环烯基乙炔4可以通过烯丙醇1轻松制备，并在与锡自由基反应时经历自由基环化（4→5）；产物5本身可以转化为烯丙醇，从而使环化序列能够重复进行。
• Pauson‐Khand Reactions with Concomitant C−O Bond Cleavage for the Preparation of 5,5‐ 5,6‐ and 5,7‐Bicyclic Ring Systems
  作者：Ding Ma、Naifeng Hu、Junli Ao、Shaoli Zang、Guo Yu、Guangxin Liang

  DOI：10.1002/adsc.202001311

  日期：2021.3.29

  Pauson‐Khand reactions (PKR) with concomitant C−O bond cleavage have been developed for construction of 5,5‐ 5,6‐ and 5,7‐bicyclic ring systems bearing complex stereochemistry. The chemistry generates intermolecular PKR‐type products in an absolute regio‐ and stereochemical control which is hardly achievable through real intermolecular Pauson‐Khand reactions. A mechanism for this Pauson‐Khand reaction

  伴随C-O键断裂的Pauson-Khand反应（PKR）已开发用于构建具有复杂立体化学的5,5-5,6-和5,7-双环体系。化学反应在绝对的区域和立体化学控制下生成分子间PKR型产物，这是通过真正的分子间Pauson-Khand反应很难实现的。基于氘标记实验，已经提出了这种Pauson-Khand反应的机制。
• Hydroxyl-Directed Nitrile Oxide Cycloaddition Reactions with Cyclic Allylic Alcohols
  作者：Nina Becker、Erick M. Carreira

  DOI：10.1021/ol7017032

  日期：2007.9.1

  Diastereoselective cycloaddition reactions between a nitrile oxide and cyclic allylic alcohols are reported. The products isolated are densely functionalized building blocks that are not otherwise easily accessed with existing methods and concepts previously established for the construction of acyclic polyketides.

  报道了一氧化氮与环状烯丙基醇之间的非对映选择性环加成反应。分离出的产物是高密度官能化的构建基块，否则，利用先前为构建无环聚酮化合物建立的现有方法和概念不容易获得这些产物。
• Chemoenzymatic routes to cyclopentenols: the role of protecting groups on stereo- and enantioselectivity
  作者：Simon Specklin、Anna Dikova、Aurélien Blanc、Jean-Marc Weibel、Patrick Pale

  DOI：10.1016/j.tetlet.2014.10.105

  日期：2014.12

  lyloxycyclopent-2-en-1-one was very efficiently obtained from diacetate of cis-cyclopent-2-en-1,3-diol using enzymatic desymmetrization with CAL-B. In these sequences, TIPS proved to be the best protecting group.

  对映体（R）-4-三异丙基甲硅烷氧基环戊-2-烯-1-酮是通过短序列获得的，这些短序列包括外消旋顺式-4-三异丙基甲硅烷氧基环戊-2-烯-1-醇的酶促拆分或顺式-环戊基-的酶促脱对称化。2-en-1,3-二醇。另外，对映体（S）-4-三异丙基甲硅烷基氧基环戊-2-烯-1-酮可以通过用CAL-B酶促脱对称从顺式-环戊-2-烯-1,3-二醇的二乙酸酯中非常有效地获得。在这些序列中，TIPS被证明是最佳的保护基团。