(Z)-4-((tert-butyldiphenylsilyl)oxy)but-2-en-1-ol | 87770-83-0

• 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: (Z)-4-((tert-butyldiphenylsilyl)oxy)but-2-en-1-ol
• 英文别名: (Z)-4-(tert-butyldiphenylsilyloxy)-2-buten-1-ol；4-tert-butyldiphenylsiloxy-2(Z)-buten-1-ol；(Z)-4-((tert-butyl)diphenylsilanyloxy)but-2-en-1-ol；(Z)-4-[tert-butyl(diphenyl)silyl]oxybut-2-en-1-ol
• CAS: 87770-83-0
• 化学式: C₂₀H₂₆O₂Si
• 分子量: 326.511
• InChiKey: QSXJMUBUMUPQAR-KHPPLWFESA-N

物化性质

• 沸点：
  402.3±45.0 °C(Predicted)
• 密度：
  1.04±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.11
• 重原子数：
  23
• 可旋转键数：
  7
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 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：

  (Z)-4-((tert-butyldiphenylsilyl)oxy)but-2-en-1-ol 在 titanium(IV) isopropylate 、 叔丁基过氧化氢 、 4 A molecular sieve 、 Celite 、 sodium acetate 、 (-)-diethyl tartrate 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 、 甲苯 为溶剂， 反应 1.0h， 生成 (-)-lyxo-(4S,5S,6S)-7-(tert-butyldiphenylsiloxy)-5,6-epoxyhept-1-en-4-ol
  参考文献：
  名称：

  A stereochemically general synthesis of 2-deoxyhexoses via the asymmetric allylboration of 2,3-epoxy aldehydes

  摘要：

  A stereochemically general strategy for the synthesis of 2-deoxyhexoses is described. This new approach involves the asymmetric allylboration of epoxy aldehydes 12 and 13, prepared via the Sharpless asymmetric epoxidation reaction, as a means of establishing the stereochemistry of the sugar backbone. Thus, the matched double asymmetric allylborations of 12 and 13 using tartrate allylboronates (R,R)- and (S,S)-7, respectively, provide erythro epoxy alcohols 14 and 16 with excellent diastereoselectivity ( > 96:4) and enantioselectivity (greater-than-or-equal-to 96% ee). The mismatched double asymmetric reactions of 12 and 13 using (S,S)- and (R,R)-7, respectively, provided the diastereomeric threo epoxy alcohols 15 and 17 with lower (ca. 75:25) but still synthetically useful selectivity. The enantiomeric purity of the major diastereomer in each of these reactions was determined to be greater than that of the epoxy aldehyde precursors. Epoxy alcohols 14 and 16 were converted with excellent selectivity to the l-arabino (21) and l-xylo (26) tetrols via neighboring group assisted alpha-substitution reactions of the derived phenylurethane derivatives 18 and 23. Stereochemically complementary beta-opening reactions were accomplished by treating primary alcohols 38, 40, 42, and 44 [prepared from 14-17, respectively, by ethoxyethylation of C(4)-OH and removal of the C(7)-tert-butyldiphenylsilyl (TBDPS) ethers] with NaOH in aqueous t-BuOH at reflux. Acid-catalyzed hydrolysis of the C(4)-ethoxyethyl ethers then provided tetrols d-35 (from 14), d-21 (from 15), d-30 (from 16), and d-26 (from 17), each with excellent stereoselectivity. These tetrols were isolated and fully characterized as the tetraacetate derivatives 36, 22, 31, and 27, respectively. These beta-opening reactions proceed by way of an epoxide migration (29 to 33) that inverts the stereochemistry at C(6) and activates C(7) toward nucleophilic attack. It is necessary that the C(4) hydroxyl be protected in three of the four stereoisomeric series to minimize competitive epoxide migration pathways (cf. 29 to 32a). arabino tetrol 21 and lyxo tetrol 30 were converted to 2-deoxyglucose and 2-deoxygalactose, respectively, by a standard ozonolytic sequence and then to 2-deoxyglucitol pentaacetate (45) and 2-deoxygalactitol pentaacetate (46) via NaBH4 reduction of the 2-deoxy sugars, thereby confirming all stereochemical assignments. The epoxide beta-opening technology was also applied to epoxy benzyl ether 47 (prepared from 14) and epoxy BOM ether 49 (deriving from 16). These reactions provide tetrol derivatives 48 and 50, respectively, in which the C(4)- and C(5)-hydroxyl functionality are suitably differentiated for use in subsequent synthetic sequences.

  DOI：

  10.1021/jo00004a053
• 作为产物：
  描述：

  tert-butyl-[(Z)-4-[tert-butyl(dimethyl)silyl]oxybut-2-enoxy]-diphenylsilane 在 tris-(4-bromophenyl)aminium hexachloroantimonate 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以99%的产率得到(Z)-4-((tert-butyldiphenylsilyl)oxy)but-2-en-1-ol
  参考文献：
  名称：

  A mild and efficient cleavage of tert-butyldimethylsilyl (TBS) and tetrahydropyranyl (THP) ethers using a catalytic amount of

  摘要：

  A mild and efficient method for the deprotection of the TBS and THP ethers is described. A wide variety of TBS ethers as well as THP ethers can be easily deprotected to the corresponding parent hydroxyl compounds by employing a catalytic amount of tris(4-bromophenyl)aminium hexachloroantimonate (TBPA(+center dot)SbCl(6)(-)) in methanol at room temperature in good yield. (C) 2008 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2008.03.149

文献信息

• A short convergent synthesis of the [3.2.1]dioxabicyclooctane subunit of sorangicin A via regioselective epoxide opening
  作者：Sadagopan Raghavan、Satyanarayana Nyalata

  DOI：10.1016/j.tet.2018.01.036

  日期：2018.3

  In this paper, we disclose the synthesis of the dioxabicyclo[3.2.1]octane subunit of the potent antibiotic sorangicin A. The synthesis was achieved in a convergent manner in 8 steps. Regio- and stereoselective intermolecular epoxide opening, ring-closing metathesis and iodo-etherification are key steps. cis-2-Butene diol has been employed as a common staring material.

  在本文中，我们公开了强效抗生素Sorangicin A的二氧杂双环[3.2.1]辛烷亚基的合成。该合成以收敛的方式通过8个步骤完成。区域和立体选择性分子间环氧化物的开环，闭环复分解和碘醚化是关键步骤。顺式-2-丁烯二醇已被用作普通的凝视材料。
• Copper(II)‐Mediated Activation of Sugar Oxazolines: Mild and Efficient Synthesis of β‐Glycosides of <i>N</i> ‐Acetylglucosamine
  作者：Valentin Wittmann、Dirk Lennartz

  DOI：10.1002/1099-0690(200204)2002:8<1363::aid-ejoc1363>3.0.co;2-#

  日期：2002.4

  2-Methyl-(3,4,6-tri-O-acetyl-1,2-dideoxy-α-D-glucopyrano)[2,1-d]-2-oxazoline (5) was reacted with glycosyl acceptors bearing primary (6, 8, 10, 20) or secondary hydroxy groups (12, 14, 16, 18) in the presence of anhydrous cupric bromide or cupric chloride at elevated temperature to provide 2-acetamido-2-deoxy-β-D-glucopyranosides in 36−92% yield. The reaction conditions are milder than those previously

  使2-甲基-（3,4,6-三-O-乙酰基-1,2-二脱氧-α-D-吡喃吡喃）[2,1 - d ] -2-恶唑啉（5）与带有伯基的糖基受体反应（6，8，10，20）或仲羟基基团（12，14，16，18）在无水溴化铜或氯化铜的存在下，在升高的温度，以提供2-乙酰氨基-2-脱氧-3-β-d-吡喃葡萄糖苷收率为36-92％。该反应条件比以前描述的使用p进行恶唑啉活化的条件温和-甲苯磺酸或氯化铁。用三甲基硅烷基叠氮化物（22）和CuCl 2处理恶唑啉可产生2-乙酰氨基-3,4,6-三-O-乙酰基-2-脱氧-β-D-吡喃葡萄糖基叠氮化物（23），产率为69％。（©Wiley-VCH Verlag GmbH，69451 Weinheim，Germany，2002）
• [EN] COMPOUNDS THAT INHIBIT MCL-1 PROTEIN<br/>[FR] COMPOSÉS INHIBANT LA PROTÉINE MCL-1
  申请人：AMGEN INC

  公开号：WO2017147410A1

  公开（公告）日：2017-08-31

  Provided herein are myeloid cell leukemia 1 protein (Mcl-1) inhibitors, methods of their preparation, related pharmaceutical compositions, and methods of using the same. For example, provided herein are compounds of Formula I, and pharmaceutically acceptable salts thereof and pharmaceutical compositions containing the compounds. The compounds and compositions provided herein may be used, for example, in the treatment of diseases or conditions, such as cancer.

  本文提供了髓样细胞白血病1蛋白（Mcl-1）抑制剂，其制备方法，相关的药物组合物，以及使用这些物质的方法。例如，本文提供了化合物I的公式，及其药用盐和含有这些化合物的药物组合物。本文提供的化合物和组合物可以用于治疗癌症等疾病或症状。
• A Cycloaddition Cascade Approach to the Total Synthesis of (−)-FR182877
  作者：David A. Evans、Jeremy T. Starr

  DOI：10.1021/ja037643+

  日期：2003.11.1

  entire structure was established using two (4R)-4-benzyl-2-oxazolidinone-mediated boron aldol reactions. A 19-membered macrocarbocycle was synthesized by the coupling of two fragments using a regioselective Suzuki coupling (17 + 23 --> 26; 84%) and macrocyclization of a beta-keto ester (30 --> 31; 77%). Oxidation of 31 triggered a sequence of stereoselective transannular Diels-Alder reactions (32 -->34;

  已实现细胞毒性天然产物 (-)-FR182877 (1) 的不对称合成。使用两个 (4R)-4-benzyl-2-oxazolidinone 介导的硼醛醇反应建立了整个结构的手性。通过使用区域选择性 Suzuki 偶联 (17 + 23 --> 26; 84%) 和 β-酮酯的大环化 (30 --> 31; 77%) 偶联两个片段来合成 19 元大碳环。31 的氧化触发了一系列立体选择性跨环 Diels-Alder 反应（32 --> 34；63%），在关键的构建事件中形成了四个新环和七个新立体中心。该五环中间体随后转化为 (-)-FR182877。对跨环 Diels-Alder 环加成级联进行了半经验计算，以确定不对称诱导的起源。
• Direct Access to Furanosidic Eight-Membered Ulosonic Esters from cis-α,β-Epoxy Aldehydes
  作者：Claudia H. Sugisaki、Yvan Ruland、Michel Baltas

  DOI：10.1002/ejoc.200390108

  日期：2003.2

  cis-α,β-epoxy aldehydes with ethyl 2-(trimethylsilyloxy)-2-propenoate in the presence of boron trifluoride−diethyl ether. An X-ray crystallographic structure of a bicycle (compound 33a) was obtained and used to determine the absolute configurations of the different stereogenic centers and thus the diastereoselective preference of the aldol reaction (syn) and the regioselectivity of the epoxide ring-opening

  通过用 2-（三甲基甲硅烷氧基）-2-丙烯酸乙酯处理不同（或未）保护的 γ,δ-双（甲硅烷氧基）顺式-α,β-环氧醛，在以下物质存在下直接获得辛糖酸的双环前体三氟化硼-乙醚。获得了自行车（化合物 33a）的 X 射线晶体结构，并用于确定不同立体中心的绝对构型，从而确定羟醛反应（syn）的非对映选择性偏好和环氧化物开环的区域选择性（C -6 原子）。研究了双环化合物的官能化和开放，以提供呋喃糖苷形式的 octulosonic 类似物。已经合成了 octulosonic 8-磷酸盐类似物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)