2-[(E)-1-(tert-Butyl-dimethyl-silanyloxy)-propenylsulfanyl]-pyridine | 152899-67-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 2-[(E)-1-(tert-Butyl-dimethyl-silanyloxy)-propenylsulfanyl]-pyridine
• 英文别名: Tert-butyl-dimethyl-(1-pyridin-2-ylsulfanylprop-1-enoxy)silane
• CAS: 152899-67-7
• 化学式: C₁₄H₂₃NOSSi
• 分子量: 281.494
• InChiKey: NIFOBFXETWIQDZ-UHFFFAOYSA-N

物化性质

• 沸点：
  334.9±38.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.06
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  47.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  癸醛 、 2-[(E)-1-(tert-Butyl-dimethyl-silanyloxy)-propenylsulfanyl]-pyridine 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 以35%的产率得到4-nonyl-3-methyloxetan-2-one
  参考文献：
  名称：

  外消旋和旋光的氧杂环丁烷-2-酮（β-内酯）的合成及其对HMG-CoA合酶的抑制作用。

  摘要：

  研究了C3-未取代和C3-甲基取代的氧杂环丁烷-2-酮（β-内酯）的同源系列，它们是酵母3-羟基-3-甲基戊二酰辅酶A（HMG-CoA）合酶的潜在抑制剂。研究了几种报道的外消旋β-内酯合成方法，以制备目标系列。此外，研究了由Et2AlCl与（1R，2R）-2-[[（二苯基）羟甲基]环己-1-醇组合制得的新型铝基路易斯酸，用于醛和三甲基甲硅烷基烯酮的不对称[2 + 2]环加成反应。该路易斯酸显示出良好的反应性，但是对映选择性可变（22-85％ee）。在使用来自酿酒酵母的天然和重组HMG-CoA合酶进行的体外分析中，在C4处被直链烷基链单取代的氧杂环丁烷-2-酮的IC50随链长增加至10个碳原子而单调下降，然后对于更长的链迅速上升。3-甲基-4-烷基-氧杂环丁烷-2-酮的反式异构体显示出相似的趋势，但IC50降低了1.3-5.6倍。结果暗示该酶中的大量疏水口袋与氧杂环丁烷-2-酮抑制剂的C-3和C-4取代基相互作用。

  DOI：

  10.1016/s0968-0896(98)00114-x
• 作为产物：
  描述：

  2-巯基吡啶 在 三乙胺 、 lithium hexamethyldisilazane 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 反应 2.5h， 生成 2-[(E)-1-(tert-Butyl-dimethyl-silanyloxy)-propenylsulfanyl]-pyridine
  参考文献：
  名称：

  难以置信的位置的复分解：Rhizoxin D的正式全合成。

  摘要：

  本文所述的抗癌剂根霉菌素D的新方法与常规的复分解逻辑不符，根据复分解的逻辑，大环最好在双取代的烯烃位点处封闭。相反，侧接有烯丙基-OH基团的三取代C11-C12烯烃是合成的关键点。通过炔烃复分解，反式-氢锡烷基化和交叉偶联的序列，可以以高收率和优异的选择性获得该基序。由于完全相同的子结构在众多其他天然产品中也很突出，因此基础策略尽管不寻常，但可能具有更广泛的相关性。

  DOI：

  10.1002/anie.201812096

文献信息

• Mechanistic Investigations of the ZnCl₂-Mediated Tandem Mukaiyama Aldol Lactonization: Evidence for Asynchronous, Concerted Transition States and Discovery of 2-Oxopyridyl Ketene Acetal Variants
  作者：Cunxiang Zhao、T. Andrew Mitchell、Ravikrishna Vallakati、Lisa M. Pérez、Daniel Romo

  DOI：10.1021/ja209163w

  日期：2012.2.15

  The ZnCl(2)-mediated tandem Mukaiyama aldol lactonization (TMAL) reaction of aldehydes and thiopyridyl ketene acetals provides a versatile, highly diastereoselective approach to trans-1,2-disubstituted β-lactones. Mechanistic and theoretical studies described herein demonstrate that both the efficiency of this process and the high diastereoselectivity are highly dependent upon the type of ketene acetal

  ZnCl(2) 介导的醛和硫吡啶基乙烯酮缩醛的串联 Mukaiyama 羟醛内酯化 (TMAL) 反应为反式 1,2-二取代 β-内酯提供了一种通用的、高度非对映选择性的方法。此处描述的机理和理论研究表明，该方法的效率和高非对映选择性都高度依赖于所采用的乙烯酮缩醛的类型，但与乙烯酮缩醛的几何形状无关。重要的是，我们根据我们迄今为止的实验证据并进一步得到计算（B3LYP/BSI）的支持，为 ZnCl(2) 介导的 TMAL 过程与其他 Mukaiyama 羟醛反应提出了一种新颖且独特的机制途径。与常见的 [2+2] 环加成和羟醛内酯化机制的极端机制相反，TMAL 过程的研究表明醛和硫代吡啶基乙烯酮缩醛之间存在协调但不同步的过渡态。这些计算支持船状过渡状态，不同于通常调用的 Mukaiyama“开放”或 Zimmerman-Traxler“椅子状”过渡状态模型。此外，实验研究支持在醛添加之前 ZnCl(2)
• Diastereoselective aldol condensation of silyl ketene acetal of 2-pyridyl thioester with benzaldehyde
  作者：Kwee-Hyun Suh、Dong-Joon Choo

  DOI：10.1016/0040-4039(95)01231-6

  日期：1995.8

  The TiCl4-mediated aldol reaction of the (E)-O-silyl ketene-O,S-acetal derived from 2-pyridyl thioester with benzaldehyde gave exclusively syn-aldol product. In contrast, BF3-mediated reaction afforded the corresponding anti-isomer as a major product. Chelation and acyclic transition state are postulated in order to explain the observed selectivities.

  由2-吡啶基硫酯衍生的（E）-O-甲硅烷基烯酮-O，S-缩醛与苯甲醛的TiCl 4介导的醇醛缩合反应仅得到顺式-醛醇缩合产物。相反，BF 3介导的反应提供了相应的反异构体作为主要产物。假定螯合和无环过渡态是为了解释观察到的选择性。
• Optically Active Aminoalcohol Promoted Addition of 2-Pyridylthioester Boron Enolates to Imines: Enantioselective One-pot Synthesis of β-Lactams
  作者：Rita Annunziata、Maurizio Benaglia、Mauro Cinquini、Franco Cozzi、Valentina Molteni、Laura Raimondi

  DOI：10.1016/0040-4020(95)00503-z

  日期：1995.8

  The enolates derived from 2-pyridylthioesters by treatment with BCl3 . Me(2)S and enantiomerically pure aminoalcohols react with aromatic and heteroaromatic imines to afford beta-lactams in a convenient one-pot procedure and in up to 78% e.e. The aminoalcohol can be employed both as the metal ligand and as the base to generate the enolate. Among several aminoalcohols tested, N-methylephedrine turned our to be the more efficient in terms of stereoselectivity.
• Synthesis of Novel β-Lactone Inhibitors of Fatty Acid Synthase
  作者：Robyn D. Richardson、Gil Ma、Yatsandra Oyola、Manuel Zancanella、Lynn M. Knowles、Piotr Cieplak、Daniel Romo、Jeffrey W. Smith

  DOI：10.1021/jm800321h

  日期：2008.9.11

  Fatty acid synthase (FAS) is necessary for growth and survival of tumor cells and is a promising drug target for oncology. Here, we report oil the syntheses and activity of novel inhibitors of the thioesterase domain of FAS. Using the structure of orlistat as a starting point, which contains a beta-lactone as the central pharmacophore, 28 novel congeners were synthesized and examined. Structural features such as the length of the alpha- and beta-alkyl chains, their chemical composition, and arnino ester substitutions were altered and tile resulting compounds explored for inhibitory activity toward the thioesterase domain of FAS. Nineteen congeners show improved potency for FAS in biochemical assays relative to orlistat. Three of that subset, including the natural product valilactone, also display all increased potency in inducing tumor cell death and improved solubility compared to orlistat. These findings Support the idea that all orlistat congener can be optimized for use in a preclinical drug design and for clinical drug development.
• A Stereocomplementary Approach to β-Lactones:  Highly Diastereoselective Synthesis of <i>cis</i>-β-Lactones, a β-Chloro Acid, and a Tetrahydrofuran
  作者：Yingcai Wang、Cunxiang Zhao、Daniel Romo

  DOI：10.1021/ol990860o

  日期：1999.10.1

  [GRAPHICS]In the course of mechanistic studies of the ZnCl2-mediated tandem Mukaiyama aldol-lactonization reaction of aldehydes and thiopyridyl ketene acetals, a stereocomplementary reaction employing SnCl4 was discovered. This method provides a highly diastereoselective entry to cis-1,2-disubstituted beta-lactones as well as a beta-chloro carboxylic acid and a tetrahydrofuran. The former products were obtained by varying the reaction temperature. The latter product was obtained when the aldehyde substrate bore a pendant silyl ether.