(2R,3S)-2,3-Epoxy-4-(tert-butyldimethylsilyloxy)butan-1-ol

• 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: (2R,3S)-2,3-Epoxy-4-(tert-butyldimethylsilyloxy)butan-1-ol
• 英文别名: (2R,3S)-4-t-butyldimethylsilyloxy-2,3-epoxy-1-butanol；(+)-(2R,3S)-4-(tert-butyldimethylsilyloxy)-2,3-epoxybutan-1-ol；(2R,3S)-4-t-butyldimethylsiloxy-2,3-epoxy-1-butanol；((2R,3S)-3-(((tert-butyldimethylsilyl)oxy)methyl)oxiran-2-yl)methanol；[(2R,3S)-3-{[(tert-butyldimethylsilyl)oxy]methyl}oxiran-2-yl]methanol；[(2R,3S)-3-[[tert-butyl(dimethyl)silyl]oxymethyl]oxiran-2-yl]methanol
• 化学式: C₁₀H₂₂O₃Si
• 分子量: 218.368
• InChiKey: GQXMFAIYVGQEJP-BDAKNGLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.77
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  42
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2,3-Epoxy-4-(tert-butyldimethylsilyloxy)butan-1-ol 在 sodium azide 、 2,2,6,6-四甲基哌啶氧化物 、 碘苯二乙酸 、 氯化铵 作用下， 以 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 13.0h， 生成 (4S,5R,E)-ethyl 4-azido-6-(tert-butyldimethylsilyloxy)-5-hydroxyhex-2-enoate
  参考文献：
  名称：

  抗流感药（-）-oseltamivir游离碱和（-）-甲基3- epi- shikimate †的合成

  摘要：

  抗流感药物（-）-oseltamivir游离碱（7.1％的总产率; 98％ee）和3-- Epi- shikimate（-）-甲基-甲基（16％的总产率; 98％ee）的新对映体选择性合成从容易获得的原材料中进行描述。醛的无尖锐不对称环氧化和非对映选择性Barbier烯丙基化是手性结合过程中的关键反应，而环己烯羧酸酯核则是通过闭环易位反应构建的。

  DOI：

  10.1039/c2ob25635e
• 作为产物：
  描述：

  (Z)-4-(tert-butyldimethylsilyloxy)but-2-en-1-ol 在 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 生成 (2R,3S)-2,3-Epoxy-4-(tert-butyldimethylsilyloxy)butan-1-ol
  参考文献：
  名称：

  New Synthesis of the (3Z,6Z,9S,10R)-Isomers of 9,10-Epoxy-3,6-henicosadiene and 9,10-Epoxy-1,3,6-henicosatriene, Pheromone Components of the Female Fall Webworm Moth,Hyphantria cunea

  摘要：

  (3Z,6Z,9S,10R)-9,10-环氧-3,6-henicosadiene(1)和(3Z,6Z,9S,10R)-9,10-环氧-1,3,6-henicosatriene(5)、这些信息素是由 (2S,3R)-2,3-环氧-4-叔丁基二甲基硅氧基-1-丁醇 (8) 开始合成的。环氧化物 8 是通过脂肪酶催化的 (±)-8 不对称乙酰化作为关键的光学解析步骤制备的。

  DOI：

  10.1271/bbb.69.1007

文献信息

• NITROGEN CONTAINING HETEROCYCLE SUBSTITUTED BENZOXAZINE OXAZOLIDINONE COMPOUND AND PREPARATION METHOD AND USE THEREOF
  申请人：INSTITUTE OF MATERIA MEDICA .CHINESE ACADEMY OF MEDICAL SCIENCES

  公开号：US20210188871A1

  公开（公告）日：2021-06-24

  The present invention discloses a nitrogen-containing heterocyclic substituted benzoxazine oxazolidinone compound, a preparation method and use thereof in the manufacture of a medicament for treating and/or preventing infectious diseases caused by Mycobacterium tuberculosis . Specifically, the present invention relates to a compound represented by formula (I) and stereoisomer thereof, pharmaceutically acceptable salt thereof, and a pharmaceutical composition comprising the compounds of the present invention, use thereof, a method for preparing the compound, in which X 1 , X 2 , R 1 and R 2 are described in the specification.

  本发明公开了一种含氮杂环取代苯并噁嗪噁唑烷酮化合物，以及其制备方法和在制备用于治疗和/或预防由结核分枝杆菌引起的传染病药物中的用途。具体而言，本发明涉及由式（I）表示的化合物及其立体异构体，其药学上可接受的盐，以及包括本发明化合物的药物组合物，其用途，制备该化合物的方法，其中X1、X2、R1和R2如说明书中所述。
• Palladium-Promoted Neutral 1,4-Brook Rearrangement/Intramolecular Allylic Cyclization Cascade Reaction: A Strategy for the Construction of Vinyl Cyclobutanols
  作者：Hao Zhang、Shiqiang Ma、Ziyun Yuan、Peng Chen、Xingang Xie、Xiaolei Wang、Xuegong She

  DOI：10.1021/acs.orglett.7b01381

  日期：2017.7.7

  cascade reaction to build vinyl cyclobutanol rings through activation of vinyl epoxides by palladium, followed by 1,4-Brook rearrangement and intramolecular cyclization with a palladium complex of the resulting carbon anion, is described. Through this cascade reaction, several highly substituted cyclobutanol substrates were achieved in good yields with high stereoselectivities.

  描述了一种级联反应，该级联反应通过钯活化乙烯基环氧化物，然后进行1,4-Brook重排和与所得碳阴离子的钯配合物进行分子内环化，从而构建乙烯基环丁醇环。通过该级联反应，以高收率和高立体选择性获得了几种高度取代的环丁醇底物。
• Sphingolipids and Glycerolipids. Part II. Syntheses of Two Pairs of Enantiomeric C18-Sphingosines and a Palmitoyl Analogue of Gaucher Spleen Glucocerebroside.
  作者：Hirotaka SHIBUYA、Keiko KAWASHIMA、Norihiko NARITA、Masahiko IKEDA、Isao KITAGAWA

  DOI：10.1248/cpb.40.1154

  日期：——

  Sixteen kinds of chiral C4-epoxides [(-)-10a-d, (+)-10a-d, (-)-11a-d, (+)-11a-d], which are synthons in our synthetic strategy for complex lipids, have been prepared from (2Z)-2-butene-1, 4-diol (6) by employing a Sharpless asymmetric epoxidation. By using the chiral C4-epoxides [(+)-10a, (-)-10a, (-)-11a, (+)-11a] as starting compounds, two pairs of enantiomeric (D-erythro, L-erythro, D-threo, and L-threo)-C18-sphingosines (1, 2, 3, 4) have been synthesized via a regioselective ring-opening of the epoxide ring with azide anion followed by reduction of the azide group to an amino group and a Wittig reaction. Furthermore, D-erythro-C18-sphingosine (1) has been converted to a palmitoyl analogue (5a) of Gaucher spleen glucocerebroside (5) through a reaction pathway including successive condensations with palmitic acid and D-glucose.

  已合成十六种手性C4-环氧化物 [(-)-10a-d, (+)-10a-d, (-)-11a-d, (+)-11a-d]，这些化合物是我们合成复杂脂质策略中的合成子，通过使用Sharpless不对称环氧化反应，从(2Z)-2-丁烯-1, 4-二醇(6)制备而成。利用手性C4-环氧化物 [(+)-10a, (-)-10a, (-)-11a, (+)-11a] 作为起始化合物，通过环氧环的区域选择性开环反应与叠氮阴离子结合，随后将叠氮基团还原为氨基，并进行Wittig反应，合成了两对对映异构体（D-赤藓糖，L-赤藓糖，D-反式，L-反式）C18-鞘氨醇（1, 2, 3, 4）。此外，D-赤藓糖-C18-鞘氨醇（1）通过与棕榈酸和D-葡萄糖的连续缩合反应途径转化为高雪氏脾脏葡萄糖苷脂（5）的棕榈酰类似物（5a）。
• Enantioselective Synthesis of the Predominant AB Ring System of the <i>Schisandra</i> Nortriterpenoid Natural Products
  作者：Birgit Gockel、Shermin S. Goh、Emma J. Puttock、Hannah Baars、Guilhem Chaubet、Edward A. Anderson

  DOI：10.1021/ol502027m

  日期：2014.9.5

  An enantioselective synthesis of the AB ring system common to the majority of the Schisandra nortriterpenoid natural products is reported. Key steps include a stereospecific ring opening of a trisubstituted epoxide and the use of a β-lactone to enable installation of the gem-dimethyl functionality of the B ring. An acetalization strategy played a key role in a late-stage biomimetic AB ring bicyclization

  据报道，大多数五味子降冰片五萜天然产物共有的AB环系统的对映选择性合成。关键步骤包括三取代的环氧化物的立体有择的开环，以及使用β-内酯来实现B环的gem- methyl官能团的安装。缩醛化策略在后期仿生AB环双环化中起关键作用。
• Syntheses of thunbergols and α- and β-cembra-2,7,11-triene-4,6-diols
  作者：Peter C. Astles、Eric J. Thomas

  DOI：10.1039/a606551a

  日期：——

  Alkylation of the racemic sulfone 25, available from the epoxide 8, using the iodide 24 followed by reduction gives the protected hydroxy acetal 27. Selective deprotection gives the alcohol 28. This is converted into the bromide 29 which is used to alkylate the keto phosphonate 33. Hydrolysis of the alkylated keto phosphonate 30 gives the aldehyde 31 which is cyclised under mild conditions (63%) and the product treated with methylmagnesium iodide, to give the racemic thunbergols 3 and 4, in a ratio of 3∶4 = 10∶90. The laevorotatory sulfone 25 has been prepared by regioselective ring-opening of the epoxide 38 followed by hydrogenation, selective protection and functional group modification. After alkylation of this sulfone using the iodide 24 and conversion into the aldehyde 46, an asymmetric aldol condensation gives the hydroxy amide 47 which is converted directly into the hydroxy keto phosphonate 49 by reaction with an excess of lithiated dimethyl methylphosphonate. After protection of the hydroxy group, selective hydrolysis of the acetal gives the aldehyde 51 which is cyclised as before to give the naturally occurring cembratrienediols 1 and 2 after reaction with methylmagnesium iodide and deprotection.

  使用碘化物 24 对环氧化物 8 生成的外消旋砜 25 进行烷基化，然后还原，得到受保护的羟基缩醛 27。选择性脱保护得到醇 28。再将其转化为溴化物 29，用于烷基化酮基膦酸酯 33。烷基化的酮基膦酸盐 30 经水解后得到醛 31，醛 31 在温和条件下进行环化（63%），产物经甲基碘化镁处理后得到外消旋噻吩伯醇 3 和 4，比例为 3â¶4 = 10â¶90。通过环氧化物 38 的区域选择性开环，然后进行氢化、选择性保护和官能团修饰，制备出了来沃托砜 25。使用碘化物 24 将该砜烷基化并转化成醛 46 后，通过不对称醛醇缩合得到羟基酰胺 47，再通过与过量的甲基膦酸二甲酯反应直接转化成羟基酮膦酸盐 49。在保护羟基后，选择性水解缩醛得到醛 51，醛 51 与甲基碘化镁反应并脱保护后，如前环化，得到天然的 cembratrienediols 1 和 2。