(+)-epi-cytoxazone | 261381-18-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: (+)-epi-cytoxazone
• 英文别名: (4R,5S)-5-(hydroxymethyl)-4-(4-methoxyphenyl)oxazolidin-2-one；(+)-5-epi-cytoxazone；(4R,5S)-5-(hydroxymethyl)-4-(4-methoxyphenyl)-1,3-oxazolidin-2-one；(+)-4-epi-cytoxazone；(4R,5S)-(-)-epi-cytoxazone；2-Oxazolidinone, 5-(hydroxymethyl)-4-(4-methoxyphenyl)-, (4R,5S)-
• CAS: 261381-18-4
• 化学式: C₁₁H₁₃NO₄
• 分子量: 223.229
• InChiKey: BUIFCOFNXXUCMV-NXEZZACHSA-N

物化性质

• 熔点：
  121-123 °C(Solv: ethyl acetate (141-78-6))
• 沸点：
  504.7±50.0 °C(Predicted)
• 密度：
  1.246±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  67.8
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  (R)-N-(1-(4-methoxyphenyl)-2-oxoethyl)benzamide 在 盐酸 、 氢氧化钾 、 sodium hydroxide 、 sodium tetrahydroborate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 水 为溶剂， 反应 0.25h， 生成 (+)-epi-cytoxazone
  参考文献：
  名称：

  Synthesis of (−)‐Cytoxazone and (+)‐epi‐Cytoxazone: The Chiral Pool Approach

  摘要：

  Immunomodulator (-)-cytoxazone and its epimer (+)-epi-cytoxazone were synthesized starting from (D)-(-)-4-hydroxyphenylglycine. Homologation of the amino acid was achieved via the corresponding aldehyde, by a cyanohydrin reaction. The racemization of highly sensible amido aldehyde was efficiently suppressed when the oxidation of the parent aminoalcohol was performed by a modified Dess-Martin procedure.

  DOI：

  10.1081/scc-200048953

文献信息

• Proline-Catalyzed α-Aminooxylation of β-Amino Aldehydes: Access to Enantiomerically Pure syn- and anti-3-Amino-3-aryl-1,2-alkanediols
  作者：Arumugam Sudalai、V. Venkataramasubramanian、I. Kiran

  DOI：10.1055/s-0034-1379735

  日期：——

  A new synthetic method for enantioselective synthesis of syn or anti -3-amino-3-aryl-1,2-alkanediols via proline catalyzed α-aminooxylation of β-amino aldehydes are described. This methodology is successfully applied to a concise and protecting group-free asymmetric synthesis of (–)-cytoxazone, (+)- epi -cytoxazone and formal synthesis of N-thiolated 2-oxazolidinone.

  描述了一种通过脯氨酸催化 β-氨基醛的 α-氨基氧化作用对映选择性合成顺式或反-3-氨基-3-芳基-1,2-烷二醇的新合成方法。该方法已成功应用于 (-)-胞恶酮、(+)- 表 - 胞恶唑的简洁且无保护基团的不对称合成和 N-硫醇化 2-恶唑烷酮的正式合成。
• New Approach for the Stereoselective Synthesis of (+)-epi-Cytoxazone
  作者：Izabel Miranda、Suélen Sartori、Marisa Diaz、Gaspar Diaz-Muñoz

  DOI：10.21577/0103-5053.20180212

  日期：——

  The stereoselective total synthesis of (+)-epi-cytoxazone was performed satisfactorily in 8 steps, in 17% overall yield, via a novel route from 2,3-O-(3-pentylidene)-(R)-glyceraldehyde. The bulky group alkene-ketal allowed intramolecular control of the target molecule’s asymmetric centers in the dihydroxylation step by promoting the approach of OsO4 to the face opposite to that of the ketal group.

  （+）-epi-cytoxazone的立体选择性全合成反应通过新的途径由2,3-O-（3-亚戊基）-（R）-甘油醛以8个步骤令人满意地完成，总收率为17％。庞大的烯烃-缩酮基团通过促进OsO4接近与缩酮基团相对的面，从而在二羟基化步骤中允许分子内控制目标分子的不对称中心。
• A Strategy to Synthesize Taxol Side Chain and (−)-<i>epi</i> Cytoxazone via Chiral Brønsted Acid-Rh₂(OAc)₄ Co-catalyzed Enantioselective Three-Component Reactions
  作者：Yu Qian、Xinfang Xu、Liqin Jiang、Dipak Prajapati、Wenhao Hu

  DOI：10.1021/jo101559p

  日期：2010.11.5

  A new approach to synthesize optically active β-amino-α-hydroxyl acid derivatives via chiral Brønsted acid-Rh2(OAc)4 cocatalyzed three-component reactions of diazo acetates with alcohols and imines is reported. A matched reaction system was identified to give the products in moderate diastereoselectivity and good enantioselectivity. Application of this methodology is demonstrated in the efficient synthesis

  报道了一种通过手性布朗斯台德酸-Rh 2（OAc）4催化重氮乙酸酯与醇和亚胺的三组分反应合成旋光性β-氨基-α-羟基酸衍生物的新方法。确定了匹配的反应系统，以使产物具有中等的非对映选择性和良好的对映选择性。该方法的应用在紫杉醇侧链和（-）- Epi- cytoxazone的有效合成中得到了证明。
• Enantioselective synthesis of (−)-cytoxazone and (+)-epi-cytoxazone, novel cytokine modulators via Sharpless asymmetric epoxidation and l-proline catalyzed Mannich reaction
  作者：Abhimanyu S. Paraskar、Arumugam Sudalai

  DOI：10.1016/j.tet.2006.03.079

  日期：2006.6

  A short and efficient enantioselective synthesis of (−)-cytoxazone and its stereoisomer (+)-epi-cytoxazone, novel cytokine modulators, has been described with good yield and enantioselectivity. Ti-catalyzed Sharpless asymmetric epoxidation of allyl alcohol and l-proline catalyzed three-component Mannich reaction constitute the key steps in introducing stereogenicity into the molecule.

  已经描述了新型的细胞因子调节剂（-）-cytoxazone及其立体异构体（+）- epi -cytoxazone的短而有效的对映选择性合成，具有良好的收率和对映选择性。钛催化的烯丙醇的Sharpless不对称环氧化和l-脯氨酸催化的三组分曼尼希反应构成了将立体异构性引入分子的关键步骤。
• Co(iii)(salen)-catalyzed HKR of two stereocentered alkoxy- and azido epoxides: a concise enantioselective synthesis of (S,S)-reboxetine and (+)-epi-cytoxazone
  作者：R. Santhosh Reddy、Pandurang V. Chouthaiwale、Gurunath Suryavanshi、Vilas B. Chavan、Arumugam Sudalai

  DOI：10.1039/c0cc00650e

  日期：——

  The HKR of racemic syn- or anti- alkoxy- and azido epoxides catalyzed by Co(salen) complex affords a practical access to a series of enantioenriched syn- or anti- alkoxy- and azido epoxides and the corresponding 1,2-diols. This strategy has been successfully employed in the concise, enantioselective synthesis of bioactive molecules such as (S,S)-reboxetine and (+)-epi-cytoxazone.

  在 Co（salen）络合物催化下，外消旋的合成或反合成烷氧基和叠氮环氧化物的 HKR 提供了获得一系列对映体富集的合成或反合成烷氧基和叠氮环氧化物以及相应的 1,2 二醇的实用途径。这种策略已成功应用于简便、对映选择性合成生物活性分子，如 (S,S)-reboxetine 和 (+)-epi-cytoxazone 等。