(S,Z)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-N-methylmethanimine oxide | 91237-25-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S,Z)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-N-methylmethanimine oxide
• 英文别名: 1-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-N-methylmethanimine oxide
• CAS: 91237-25-1
• 化学式: C₇H₁₃NO₃
• 分子量: 159.185
• InChiKey: JQHVCDKJEKVWGX-OJYYCGRUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  47.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S,Z)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-N-methylmethanimine oxide 在 palladium dihydroxide 盐酸 、 4-二甲氨基吡啶 、 氢气 作用下， 以 苯 为溶剂， 反应 120.0h， 生成 N,O,O-triacetyl-α-epigentosaminide
  参考文献：
  名称：

  Stereoselection in acyclic systems. The synthesis of amino sugars via nitrone cycloadditions

  摘要：

  DOI：

  10.1021/ja00331a033
• 作为产物：
  描述：

  (3S,4R,5S)-5-[(4S)-2,2-二甲基-1,3-二氧戊环-4-基]-3,4-二羟基二氢-2(3H)-呋喃酮 在 sodium periodate 、 magnesium sulfate 、 三乙胺 、 sodium hydroxide 作用下， 以 二氯甲烷 、 水 为溶剂， 反应 26.0h， 生成 (S,Z)-1-(2,2-dimethyl-1,3-dioxolan-4-yl)-N-methylmethanimine oxide
  参考文献：
  名称：

  Ruthenium-Catalyzed Asymmetric N-Demethylative Rearrangement of Isoxazolidines and Its Application in the Asymmetric Total Syntheses of (−)-(1R,3S)-HPA-12 and (+)-(1S,3R)-HPA-12

  摘要：

  An asymmetric N-demethylative rearrangement of 1,2-isoxazolidines catalyzed by ruthenium is described. Enantioenriched syn-1,3-aminoalcohols as well as cis-1,3-oxazinanes, which are useful building blocks, can be efficiently prepared stereospecifically by this reaction in good yields, via the isoxazolidine intermediates in situ generated from a nitrone bearing a chiral auxiliary and styrenes. This asymmetric reaction was also applied in the asymmetric total syntheses of both (-)-(1R,3S)-HPA-12 and (+)-(1S,3R)-HPA-12.

  DOI：

  10.1021/ol503261h

文献信息

• Stereodivergent Syntheses of Highly Substituted Enantiopure 4-Alkoxy-3,6-dihydro-2H-1,2-oxazines by Addition of Lithiated Alkoxyallenes to Carbohydrate-Derived Aldonitrones
  作者：Matthias Helms、Wolfgang Schade、Robert Pulz、Toshiko Watanabe、Ahmed Al-Harrasi、Lubor Fišera、Iva Hlobilová、Gernot Zahn、Hans-Ulrich Reißig

  DOI：10.1002/ejoc.200400627

  日期：2005.3

  Additions of lithiated alkoxyallenes to D-glyceraldehyde-based nitrones 1 and 2 did not provide the expected hydroxylamine derivatives. Instead, a novel [3+3] cyclization process furnished 4-alkoxy-3,6-dihydro-2H-1,2-oxazines 9–14 with excellent syn selectivities and in moderate to good yields. Through precomplexation of the nitrones the corresponding anti-configured 1,2-oxazines 9, 10 and 13 could

  将锂化烷氧基丙二烯添加到基于 D-甘油醛的硝酮 1 和 2 中并没有提供预期的羟胺衍生物。相反，一种新的 [3+3] 环化工艺提供了具有优异顺式选择性和中等至良好产率的 4-烷氧基-3,6-二氢-2H-1,2-恶嗪 9-​​14。通过硝酮的预络合，可以以高立体选择性获得相应的反构型 1,2-恶嗪 9、10 和 13。衍生自 D-赤藓糖或 D-苏糖的硝酮 3-6 的反应通常进行较少的非对映选择性，但在路易斯酸下可以获得合理的反构型 1,2-恶嗪，如抗 17 和抗 19促销条件。D-阿拉伯糖衍生的硝酮 7 的反应也是如此，它提供了抗 1、2-恶嗪 23 和 24 具有优异的非对映选择性和良好的产率。双硝酮 8 和锂化甲氧基丙二烯提供了六种化合物的混合物，其中主要成分是 C2 对称的 Syn/syn-1,2-恶嗪 29。这些反应的非对映选择性是根据 Dondoni 之间的反应模型来解释的。有机锂化合物和硝酮。讨论了
• Zinc Iodide-Mediated Direct Synthesis of 2,3-Dihydroisoxazoles from Alkynes and Nitrones
  作者：Zu-Feng Xiao、Ting-Hui Ding、Sheng-Wei Mao、Xiao-Shan Ning、Yan-Biao Kang

  DOI：10.1002/adsc.201600044

  日期：2016.6.2

  A zinc diiodide (ZnI2)‐mediated direct synthesis of 2,3‐dihydroisoxazoles via a [3+2] cycloaddition reaction of the nitrones and non‐electron‐deficient terminal alkynes has been developed. This method was applied in the formal synthesis of HPA‐12 and aminoglucose.

  甲二碘化锌（ZnI 2）介导的2,3- dihydroisoxazoles直接合成经由所述硝酮和非缺电子末端炔烃的[3 + 2]环加成反应得到了发展。该方法用于HPA-12和氨基葡萄糖的正式合成。
• A New Diastereoselective Synthesis of Enantiomerically Pure 1,2-Oxazine Derivatives by Addition of Lithiated Methoxyallene to Chiral Nitrones
  作者：Wolfgang Schade、Hans-Ulrich Reissig

  DOI：10.1055/s-1999-2662

  日期：1999.5

  Addition of lithiated methoxyallene 2 to nitrones provided hydroxylamine derivatives which usually undergo very fast cyclization to 3,6-dihydro-2H-1,2-oxazines. Chiral nitrones 5, 8, or 10 which furnished 1,2-oxazines 6, 9, and 11 with excellent syn diastereoselectivities are of particular interest. By precomplexation of nitrone 5b with diethylaluminum chloride 1,2-oxazine 6b was produced with excellent

  将锂化的甲氧基丙二烯 2 加成到硝酮提供了羟胺衍生物，其通常会非常快速地环化为 3,6-二氢-2H-1,2-恶嗪。提供具有优异顺式非对映选择性的 1,2-恶嗪 6、9 和 11 的手性硝酮 5、8 或 10 尤其令人感兴趣。通过硝酮 5b 与二乙基氯化铝的预络合，1,2-恶嗪 6b 具有优异的抗选择性。所得的 3,5-二氢-2H-1,2-恶嗪是用于立体选择性合成多官能化合物的通用起始材料。
• Lewis acid stereocontrolled additions of a silyl ketene acetal to 2,3-di-O-isopropylidene-d-glyceraldehyde nitrones. Synthesis of l-isoxazolidinyl nucleosides
  作者：Pedro Merino、Eva M del Alamo、Maite Bona、Santiago Franco、Francisco L Merchan、Tomas Tejero、Odile Vieceli

  DOI：10.1016/s0040-4039(00)01674-9

  日期：2000.11

  The reaction of O-methyl-O-tert-butyldimethylsilyl ketene acetal with N-benzyl and N-methyl-2,3-O-isopropylidene-d-glyceraldehyde nitrones in the presence of boron trifluoride etherate afforded the corresponding isoxazolidin-5-ones in excellent yields and anti-selectivities. The obtained compounds were used as key intermediates for the synthesis of isoxazolidinyl nucleosides of the l-series.

  的反应ö甲基ö -叔丁基二甲基烯酮乙缩醛与ñ -苄基和Ñ甲基-2,3- Ö在三氟化硼醚，得到相应的异恶唑烷-5-酮存在下异亚丙基- d甘油醛硝酮具有优异的收率和抗选择性。所获得的化合物用作合成l系列异恶唑啉基核苷的关键中间体。
• Enantioselective synthesis of N,O-psiconucleosides
  作者：Ugo Chiacchio、Luisa Borrello、Daniela Iannazzo、Pedro Merino、Anna Piperno、Antonio Rescifina、Barbara Richichi、Giovanni Romeo

  DOI：10.1016/s0957-4166(03)00525-1

  日期：2003.8

  The first enantioselective synthesis Of beta-D and beta-L N,O-psiconucleosides is reported. The synthetic approach is based on the asymmetric 1.3-dipolar cycloaddition of the C-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]-N-methyl nitrone with ethyl 2-acetyl-oxyacrylate followed by Vorbruggen nucleosidation, and removal of the chiral auxiliary. Stereochemical assignments are supported by a DFT theoretical study of the cycloaddition reaction. (C) 2003 Elsevier Ltd. All rights reserved.