(3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,4,5,6-tetrahydro-2H-1,2-oxazin-4-one | 537703-93-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,4,5,6-tetrahydro-2H-1,2-oxazin-4-one
• 英文别名: (3S)-2-benzyl-3-[(4S)-2,2-dimethyl-1,3-dioxolan-4-yl]oxazinan-4-one
• CAS: 537703-93-8
• 化学式: C₁₆H₂₁NO₄
• 分子量: 291.347
• InChiKey: OPSSAWVUORPILG-HUUCEWRRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.6
• 重原子数：
  21
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.56
• 拓扑面积：
  48
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,4,5,6-tetrahydro-2H-1,2-oxazin-4-one 在 三乙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 12.0h， 生成 (2Z,4R,4'S)-4-(benzyl(methyl)amino)-4-(2,2-dimethyl[1',3']dioxolan-4'-yl)-3-methylbut-2-enal
  参考文献：
  名称：

  β-Alkoxy-γ-amino Aldehydes by Internal Redox Ring Cleavages of Carbohydrate-Derived Enantiopure 1,2-Oxazines and Preparation of Heterocycles with Aminopolyol Side Chain

  摘要：

  N-甲基化syn-或anti-构型的3,6-二氢-2H-1,2-恶嗪，然后与三乙胺处理，顺利提供了具有不同保护二醇、三醇或四醇侧链的高至优异收率的立体纯α,β-不饱和β-烷氧基-γ-氨基醛。N-O键在温和条件下断裂，涉及内部氧化还原过程。该方法也适用于四氢-2H-1,2-恶嗪，它们要么导致4-氨基酮糖或醛糖衍生物（d-山梨糖醇或d-艾杜糖醇构型）。生成的β-烷氧基烯醛部分与1,3-二羰基化合物的等价性可以通过与肼或2-氨基咪唑衍生物的缩合反应证明，提供了一系列具有立体定义和保护氨基多醇侧链的新型吡唑或咪唑并[1,2-a]嘧啶衍生物。

  DOI：

  10.1055/s-0030-1258326
• 作为产物：
  描述：

  (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-4-methoxy-3,6-dihydro-2H-1,2-oxazine 在 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 三(三甲基硅基)硅烷 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 6.0h， 生成 (3S,4'S)-2-benzyl-3-(2',2'-dimethyl-1',3'-dioxolan-4'-yl)-3,4,5,6-tetrahydro-2H-1,2-oxazin-4-one
  参考文献：
  名称：

  Synthesis of Enantiopure Amino Polyols and Pyrrolidine Derivatives from 5-Bromo-1,2-oxazin-4-ones

  摘要：

  对 3,6-二氢-2H-1,2-恶嗪 syn-1 和 anti-1 进行非对映选择性亲电溴化反应后，分别得到 5-溴-1,2-恶嗪-4-酮 2a 和 3a。 还原生成的 1,2-恶嗪-4-酮 4 和 6 可转化为不对映纯的氨基和亚氨基糖衍生物。溴官能团的亲核取代反应产生了氨基取代的 1,2-噁嗪 10。它们被转化为二氨基取代的糖衍生物。

  DOI：

  10.1055/s-2003-37121

文献信息

• Convenient Syntheses of Enantiopure 1,2-Oxazin-4-yl Nonaflates and Phosphates and Their Palladium-Catalyzed Cross-Couplings
  作者：Reinhold Zimmer、Hans-Ulrich Reissig、Nima Moinizadeh、Robby Klemme、Marcus Kansy

  DOI：10.1055/s-0033-1339509

  日期：——

  Efficient methods to prepare enantiopure 1,2-oxazin-4-yl nonaflates and phosphates were elaborated. The corresponding 1,2-oxazin-4-ones were transformed into their enolates and then quenched with nonafluorobutanesulfonyl fluoride or diphenyl chlorophosphate to provide the title compounds. Alternatively, the corresponding -bromo ketones were subjected to Perkow reactions efficiently leading to the respective enol phosphates. A variety of palladium-catalyzed cross-couplings such as Kumada-Corriu, Sonogashira, Heck reactions or borylation reactions were studied, which delivered the expected new 4-substituted 1,2-oxazine derivatives generally in satisfactory yields. A few typical subsequent transformations were studied including a copper-catalyzed [3+2] cycloaddition with a galactose-derived azide. They demonstrate the synthetic potential of the newly prepared enantiopure 4-substituted 1,2-oxazines.
• β-Alkoxy-γ-amino Aldehydes by Internal Redox Ring Cleavages of Carbohydrate-Derived Enantiopure 1,2-Oxazines and Preparation of Heterocycles with Aminopolyol Side Chain
  作者：Hans-Ulrich Reissig、Ahmed Al-Harrasi、Léa Bouché、Reinhold Zimmer

  DOI：10.1055/s-0030-1258326

  日期：2011.1

  N-Methylation of syn- or anti-configured 3,6-dihydro-2H-1,2-oxazines and subsequent treatment with triethylamine smoothly provided enantiopure α,β-unsaturated β-alkoxy-γ-amino aldehydes bearing different protected diol, triol, or tetrol side chains in good to excellent yields. The N-O bond cleavage occurs under mild conditions and involves an internal redox process. The method is also applicable to tetrahydro-2H-1,2-oxazines, which either lead to 4-amino ketose or aldose derivatives (d-sorbose or d-idose configuration). The equivalency of the generated β-alkoxyenal moiety with 1,3-dicarbonyl compounds could be demonstrated by condensation reactions with hydrazine or 2-aminoimidazole derivatives providing a series of new pyrazole or imidazo[1,2-a]pyrimidine derivatives with stereodefined and protected aminopolyol side chains.

  N-甲基化syn-或anti-构型的3,6-二氢-2H-1,2-恶嗪，然后与三乙胺处理，顺利提供了具有不同保护二醇、三醇或四醇侧链的高至优异收率的立体纯α,β-不饱和β-烷氧基-γ-氨基醛。N-O键在温和条件下断裂，涉及内部氧化还原过程。该方法也适用于四氢-2H-1,2-恶嗪，它们要么导致4-氨基酮糖或醛糖衍生物（d-山梨糖醇或d-艾杜糖醇构型）。生成的β-烷氧基烯醛部分与1,3-二羰基化合物的等价性可以通过与肼或2-氨基咪唑衍生物的缩合反应证明，提供了一系列具有立体定义和保护氨基多醇侧链的新型吡唑或咪唑并[1,2-a]嘧啶衍生物。
• Synthesis of Enantiopure Amino Polyols and Pyrrolidine Derivatives from 5-Bromo-1,2-oxazin-4-ones
  作者：Hans-Ulrich Reissig、Robert Pulz、Wolfgang Schade

  DOI：10.1055/s-2003-37121

  日期：——

  Diastereoselective electrophilic bromination of 3,6-dihydro-2H-1,2-oxazines syn-1 and anti-1 led to 5-bromo-1,2-oxazin-4-ones 2a and 3a, respectively. Reduction furnished 1,2-oxazin-4-ones 4 and 6 which could be transformed into enantiopure amino and imino sugar derivatives. Nucleophilic substitution of the bromo functionality gave amino substituted 1,2-oxazines 10. They were converted into diamino substituted sugar derivatives.

  对 3,6-二氢-2H-1,2-恶嗪 syn-1 和 anti-1 进行非对映选择性亲电溴化反应后，分别得到 5-溴-1,2-恶嗪-4-酮 2a 和 3a。 还原生成的 1,2-恶嗪-4-酮 4 和 6 可转化为不对映纯的氨基和亚氨基糖衍生物。溴官能团的亲核取代反应产生了氨基取代的 1,2-噁嗪 10。它们被转化为二氨基取代的糖衍生物。