2-(trimethylsilyl)ethyl N-hydroxycarbamate | 134262-94-5

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 英文名称: 2-(trimethylsilyl)ethyl N-hydroxycarbamate
• 英文别名: 2-trimethylsilylethyl N-hydroxycarbamate
• CAS: 134262-94-5
• 化学式: C₆H₁₅NO₃Si
• 分子量: 177.275
• InChiKey: QLISFPUPYNEPGT-UHFFFAOYSA-N

物化性质

• 沸点：
  276.0±23.0 °C(Predicted)
• 密度：
  1.023±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.44
• 重原子数：
  11
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  58.6
• 氢给体数：
  2
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl N-hydroxycarbamate 在 三苯基膦氢溴酸盐 、 sodium hydride 、 sodium cyanoborohydride 、 magnesium sulfate 、 potassium carbonate 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 乙硫醇 、 肼 作用下， 以 甲醇 、 乙醇 、 二氯甲烷 、 异丙醇 、 苯 为溶剂， 反应 53.57h， 生成 (4-methoxyphenyl)methyl 4,6-dideoxy-4-<<2,4,6-trideoxy-3-O-<(1,1-dimethylethyl)dimethylsilyl>-4-(methylthio-β-D-ribo-hexopyranosyl)oxy><2-(trimethylsilyl)ethoxycarbonyl>amino>-2-O-<2,4-dideoxy-3-O-methyl-4-<(1-methylethyl)amino>-α-L-threo-pentopyra>..
  参考文献：
  名称：

  Studies Related to the Carbohydrate Sectors of Esperamicin and Calicheamicin: Definition of the Stability Limits of the Esperamicin Domain and Fashioning of a Glycosyl Donor from the Calicheamicin Domain

  摘要：

  The core trisaccharide regions of esperamicin and the aryltetrasaccharide region of calicheamicin have been synthesized. The minimum protection modalities necessary to stabilize structures against rearrangement to an isomeric azafuranose series were ascertained (see compounds 12 and 65). Deprotection of the 2-(trimethylsilyl)ethoxycarbonyl carbamate from 65 led to azafuranose 14 characterized as methyl glycoside 15. Using this insight, it was possible to fashion, for the first time, a pre-glycosyl donor (see compound 128) corresponding to the complete arylsaccharide sector of calicheamicin gamma(1)(I) at the oxidation level of the domain. Among the key assembly strategies were the conversion of alpha-thiophenylpseudoglycals to allal derivatives (see 44 --> 45); the interfacing of epoxide-mediated glycosylation with iodoglycosylation (see 30 --> 47 --> 48); the synthesis of hydroxylamine glycosides via triflate displacement (see 61 + 91 --> 101); and a new route to p-hydroxybenzonitriles (see formation of 86).

  DOI：

  10.1021/ja00126a013
• 作为产物：
  描述：

  2-三甲基甲硅烷基乙氧基羰酰氯 在 sodium hydroxide 、 盐酸羟胺 作用下， 以 1,4-二氧六环 为溶剂， 反应 14.0h， 以60%的产率得到2-(trimethylsilyl)ethyl N-hydroxycarbamate
  参考文献：
  名称：

  Studies Related to the Carbohydrate Sectors of Esperamicin and Calicheamicin: Definition of the Stability Limits of the Esperamicin Domain and Fashioning of a Glycosyl Donor from the Calicheamicin Domain

  摘要：

  The core trisaccharide regions of esperamicin and the aryltetrasaccharide region of calicheamicin have been synthesized. The minimum protection modalities necessary to stabilize structures against rearrangement to an isomeric azafuranose series were ascertained (see compounds 12 and 65). Deprotection of the 2-(trimethylsilyl)ethoxycarbonyl carbamate from 65 led to azafuranose 14 characterized as methyl glycoside 15. Using this insight, it was possible to fashion, for the first time, a pre-glycosyl donor (see compound 128) corresponding to the complete arylsaccharide sector of calicheamicin gamma(1)(I) at the oxidation level of the domain. Among the key assembly strategies were the conversion of alpha-thiophenylpseudoglycals to allal derivatives (see 44 --> 45); the interfacing of epoxide-mediated glycosylation with iodoglycosylation (see 30 --> 47 --> 48); the synthesis of hydroxylamine glycosides via triflate displacement (see 61 + 91 --> 101); and a new route to p-hydroxybenzonitriles (see formation of 86).

  DOI：

  10.1021/ja00126a013

文献信息

• Osmium-Catalyzed Vicinal Oxyamination of Alkenes by <i>N</i>-(4-Toluenesulfonyloxy)carbamates
  作者：Masruri、Anthony C. Willis、Malcolm D. McLeod

  DOI：10.1021/jo301372y

  日期：2012.10.5

  N-(4-Toluenesulfonyloxy)carbamates based on a range of common amine protecting groups serve as preformed nitrogen sources in the intermolecular osmium-catalyzed oxyamination reaction of a variety of mono-, di-, and trisubstituted alkenes. The reactions occur with low catalyst loadings and good yields and afford high regioselectivity for unsymmetrically substituted alkenes.

  在一系列单，二和三取代烯烃的分子间催化的氧化胺化反应中，基于一系列常见胺保护基的N-（4-甲苯磺酰氧基）氨基甲酸酯用作预制的氮源。该反应以低的催化剂负载量和良好的收率进行，并且对于不对称取代的烯烃提供高的区域选择性。
• An Asymmetric Synthesis of the Tricyclic Core and a Formal Total Synthesis of Roseophilin via an Enyne Metathesis
  作者：Barry M. Trost、George A. Doherty

  DOI：10.1021/ja9941781

  日期：2000.4.1

  the stage for the key metathesis reaction. Platinum-catalyzed enyne metathesis via a formal [2 + 2] cycloaddition to a cyclobutene followed by conrotatory ring opening created the corresponding bicyclo[10.2.1]pentadeca-1(15),2-diene. Regioselective epoxidation of the less reactive double bond of the 1,3-diene was accomplished by 1,4-bromohydrin formation followed by base. Cuprate opening regio- and

  Roseophilin 是一种具有显着抗肿瘤活性的新型五环结构，从 3-环十一碳烯基羧酸开始的正式合成已经完成。酸通过乙烯酮非对映选择性地转化为相应的薄荷醇酯，乙烯酮又提供(S)-3-环十一碳烯基甲醛。由三溴化硼和 (S,S)-二苯乙烯二胺的双-对甲苯磺酰胺原位制备的不对称硼试剂促进与炔丙基三苯基锡烷的非对映选择性炔丙基化反应得到 (1S,1'R)-1-cycloundec-2'-enylbut-3 -yn-1-ol 为关键的复分解反应奠定了基础。铂催化的烯炔复分解反应通过正式的 [2 + 2] 环加成反应到环丁烯，然后旋转开环产生相应的双环 [10.2.1]pentadeca-1(15),2-二烯。1,3-二烯的反应性较低的双键的区域选择性环氧化是通过形成1,4-溴醇，然后形成碱来完成的。铜酸盐开口区域和立体定向安装...
• From 1-(Silyloxy)Butadiene to 4-Amino-4-Deoxy-DL-Erythrose and to 1-Amino-1-Deoxy-DL-Erythritol Derivativesvia Hetero-Diels-Alder Reactions with Acylnitroso Dienophiles
  作者：Albert Defoin、Joaquim Pires、Jacques Streith

  DOI：10.1002/hlca.19910740806

  日期：1991.12.11

  Acylnitroso dienophiles 4 reacted instantly with 1-(silyloxy)butadiene 5α and led in good yield to the regioisomeric cycloadducts 6 (major) and 7 (minor; Scheme 2, Table 1). cis-Hydroxylation of these primary cycloadducts with OsO4 (catalyst) occurred stereospecifically and in high yield (8 and 9, resp.; Scheme 2). It was followed by reductive ring cleavage to give either 1-amino-1-deoxy-DL-erythritol

  酰基亚硝基亲二烯体4立即与1-（甲硅烷氧基）丁二烯5α反应，并以良好的产率产生区域异构体环加合物6（主要）和7（次要；方案2，表1）。这些一级环加合物与OsO 4（催化剂）的顺式羟基氧化立体定向且高收率发生（8和9，分别；方案2）。根据还原剂的性质，其后进行还原性环裂解分别生成1-氨基-1-脱氧-DL-赤藓糖醇或4-氨基-4-脱氧-DL-赤藓糖衍生物10和14（方案3和4）。
• Chiral N-dienyl-L-pyroglutamic esters in asymmetric hetero-Diels-Alder reactions with acylnitroso dienophiles
  作者：Jean-Bernard Behr、Albert Defoin、Joaquim Pires、Jacques Streith、Ludwig Macko、Margaretha Zehnder

  DOI：10.1016/0040-4020(95)01111-0

  日期：1996.2

  Asymmetric Diels-Alder reaction of the N-dienyl-L-pyroglutamic esters 1a-h with acyl nitroso dienophiles 4a-h gave diastereoisomeric adducts 6a-n, 7a-n with 12–90 % de, depending on solvents and temperature. An interpretation was gived. The “allylic effect” ( MO interactions) was found to be effective to account for the conformations of the adducts.

  的N二烯基- L-焦酯的不对称狄尔斯-阿尔德反应1A-H与酰基亚硝基亲二烯体4A-H ，得到非对映体加合物6A-n中，图7a-N与12-90％去，这取决于溶剂和温度。作出了解释。发现“烯丙基效应”（MO相互作用）可有效解释加合物的构象。
• 一种羧胺三唑代谢产物、制备方法及应用
  申请人：广东银珠医药科技有限公司

  公开号：CN117756728A

  公开（公告）日：2024-03-26

  本发明公开了一种羧胺三唑代谢产物，即1‑（3,5‑二氯‑4‑（4‑氯苯甲酰基）苄基）‑5‑（羟胺）‑1H‑1,2,3‑三唑‑4‑甲酰胺，以及其制备方法和在抗肿瘤、抗自身炎症性疾病方面的用途。通过肝微粒体研究得到了羧胺三唑在体内的氧化代谢产物，并利用羧胺三唑经过硼酸钠氧化生成中间体，中间体经锌粉还原得到目标化合物，合成步骤简单，且反应条件温和，适合放大生产；且本发明得到的羧胺三唑代谢产物具有较好的抗肿瘤和降低炎症细胞因子的作用，具有抗癌和抗自身炎症性疾病的潜在用途。