N-tert-butoxycarbonyl (4S)-4-[1'-oxo-(2'E,4'E)-hexadecadienyl]-2,2-dimethyl-1,3-oxazolidine | 410082-68-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: N-tert-butoxycarbonyl (4S)-4-[1'-oxo-(2'E,4'E)-hexadecadienyl]-2,2-dimethyl-1,3-oxazolidine
• 英文别名: (-)-(S)-tert-butyl 4-((2E,4E)-hexadeca-2,4-dienoyl)-2,2-dimethyloxazolidine-3-carboxylate；tert-butyl (4S)-4-[(2E,4E)-hexadeca-2,4-dienoyl]-2,2-dimethyl-1,3-oxazolidine-3-carboxylate
• CAS: 410082-68-7
• 化学式: C₂₆H₄₅NO₄
• 分子量: 435.648
• InChiKey: GOGIHYFDAIPPPW-HPLWMJBBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8
• 重原子数：
  31
• 可旋转键数：
  15
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-tert-butoxycarbonyl (4S)-4-[1'-oxo-(2'E,4'E)-hexadecadienyl]-2,2-dimethyl-1,3-oxazolidine 在 盐酸 作用下， 以 甲醇 为溶剂， 反应 1.0h， 以50%的产率得到(2S,4E,6E)-2-amino-3-oxo-4,6-octadecadien-1-ol hydrochloride
  参考文献：
  名称：

  短链3-酮神经酰胺，针对人白血病HL-60细胞的强凋亡诱导剂。

  摘要：

  神经酰胺充当凋亡信号传导过程的第二信使。包含C-3，C-4和C-5碳的烯丙醇部分对于此功能至关重要。已经提出该醇部分在线粒体中被氧化成羰基部分，并产生活性氧。然而，对于这样推测的3-酮神经酰胺的细胞凋亡性能尚无确定的先例。在这项工作中，我们合成了三种不同类型的短链3-酮神经酰胺，即（2S，4E）-2-乙酰氨基-3-氧代-4-十八烯-1-醇（A），（2S，4E ，6E）-2-乙酰氨基-3-oxo-4,6-octadecadien-1-ol（B）和（2S，4E）-2-乙酰氨基-1-甲氧基-3-oxo-4-octadecene（C）并证明这些3-酮神经酰胺能够诱导人白血病HL-60细胞有效凋亡。特别是两种单烯化合物 A和C比相应的醇类似物N-乙酰基-D-赤型-鞘氨醇强得多。DNA片段化，caspase-3激活和线粒体细胞色素c释放的观察提供了线粒体凋亡的确凿证据，并且还讨论了外源性谷胱甘肽对这些现象的影响。

  DOI：

  10.1016/j.bmc.2007.02.008
• 作为产物：
  描述：

  (S)-(-)-3-BOC-4-甲氧羰基-2,2-二甲基-1,3-恶唑烷 在 正丁基锂 、 potassium carbonate 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 72.0h， 生成 N-tert-butoxycarbonyl (4S)-4-[1'-oxo-(2'E,4'E)-hexadecadienyl]-2,2-dimethyl-1,3-oxazolidine
  参考文献：
  名称：

  Synthesis of New Trans Double-Bond Sphingolipid Analogues:  Δ^4,6 and Δ⁶ Ceramides

  摘要：

  Unsaturation was introduced at Delta(4.6) and Delta(6) of the sphingoid chain of naturally occurring ceramide 1 via a beta-keto sulfoxide (12) and sulfone (18) derived from N-Boe-L-serine methyl ester acetonide (9), affording two novel ceramide analogues, (2S,3R)-2-octanoylamidooetadeca-(4E,6E)-diene-1,3-diol (2) and (2S,3R)-2-octanoylamidooetadec-(6E)-ene-1,3-diol (3). After C-alkylation of 12 with (E)1-bromo-2-tetradecene (8), a trans double bond was installed by elimination of PhS(O)H, providing conjugated dienone oxazolidine 13. Reaction of 18 with 8, followed by desulfonation (AI(Hg)), afforded keto-oxazolidine 20, which bears a (E)-Delta(6) double bond. The syntheses of analogues 2 and 3 from ketones 13 and 20, respectively, were completed by the following sequence of reactions: diastereoselective reduction (NaBH4/CeCl3 or DIBAL-H), hydrolysis of the oxazolidine ring, liberation of the amino group, and installation of the N-amide group.

  DOI：

  10.1021/jo0162639

文献信息

• Oxidative Heck Vinylation for the Synthesis of Complex Dienes and Polyenes
  作者：Jared H. Delcamp、Paul E. Gormisky、M. Christina White

  DOI：10.1021/ja402891m

  日期：2013.6.12

  We introduce an oxidative Heck reaction for selective complex diene and polyene formation. The reaction proceeds via oxidative Pd(II)/sulfoxide catalysis that retards palladium-hydride isomerizations which previously limited the Heck manifold's capacity for furnishing stereodefined conjugated dienes. Limiting quantities of nonactivated terminal olefins (1 equiv) and slight excesses of vinyl boronic esters (1.5 equiv) that feature diverse functionality can be used to furnish complex dienes and polyenes in good yields and excellent selectivities (generally E:Z = >20:1; internal:terminal = >20:1). Because this reaction only requires prior activation of a single vinylic carbon, improvements in efficiency are observed for synthetic sequences relative to ones featuring reactions that require activation of both coupling partners.
• Short-chain 3-ketoceramides, strong apoptosis inducers against human leukemia HL-60 cells
  作者：Hideki Azuma、So Ijichi、Mayuko Kataoka、Akira Masuda、Takayuki Izumi、Tetsuya Yoshimoto、Taro Tachibana

  DOI：10.1016/j.bmc.2007.02.008

  日期：2007.4

  leukemia HL-60 cells. In particular, the two monoenoic compounds, A and C, are far more powerful than the corresponding alcoholic analogue, N-acetyl-D-erythro-sphingosine. Observations of DNA fragmentation, caspase-3 activation, and cytochrome c release from mitochondria provide substantiated evidence for mitochondrial apoptosis and the effects of exogenous glutathione on these phenomena are also discussed

  神经酰胺充当凋亡信号传导过程的第二信使。包含C-3，C-4和C-5碳的烯丙醇部分对于此功能至关重要。已经提出该醇部分在线粒体中被氧化成羰基部分，并产生活性氧。然而，对于这样推测的3-酮神经酰胺的细胞凋亡性能尚无确定的先例。在这项工作中，我们合成了三种不同类型的短链3-酮神经酰胺，即（2S，4E）-2-乙酰氨基-3-氧代-4-十八烯-1-醇（A），（2S，4E ，6E）-2-乙酰氨基-3-oxo-4,6-octadecadien-1-ol（B）和（2S，4E）-2-乙酰氨基-1-甲氧基-3-oxo-4-octadecene（C）并证明这些3-酮神经酰胺能够诱导人白血病HL-60细胞有效凋亡。特别是两种单烯化合物 A和C比相应的醇类似物N-乙酰基-D-赤型-鞘氨醇强得多。DNA片段化，caspase-3激活和线粒体细胞色素c释放的观察提供了线粒体凋亡的确凿证据，并且还讨论了外源性谷胱甘肽对这些现象的影响。
• Synthesis of New Trans Double-Bond Sphingolipid Analogues:  Δ^4,6 and Δ⁶ Ceramides
  作者：Jiong Chun、Guoqing Li、Hoe-Sup Byun、Robert Bittman

  DOI：10.1021/jo0162639

  日期：2002.4.1

  Unsaturation was introduced at Delta(4.6) and Delta(6) of the sphingoid chain of naturally occurring ceramide 1 via a beta-keto sulfoxide (12) and sulfone (18) derived from N-Boe-L-serine methyl ester acetonide (9), affording two novel ceramide analogues, (2S,3R)-2-octanoylamidooetadeca-(4E,6E)-diene-1,3-diol (2) and (2S,3R)-2-octanoylamidooetadec-(6E)-ene-1,3-diol (3). After C-alkylation of 12 with (E)1-bromo-2-tetradecene (8), a trans double bond was installed by elimination of PhS(O)H, providing conjugated dienone oxazolidine 13. Reaction of 18 with 8, followed by desulfonation (AI(Hg)), afforded keto-oxazolidine 20, which bears a (E)-Delta(6) double bond. The syntheses of analogues 2 and 3 from ketones 13 and 20, respectively, were completed by the following sequence of reactions: diastereoselective reduction (NaBH4/CeCl3 or DIBAL-H), hydrolysis of the oxazolidine ring, liberation of the amino group, and installation of the N-amide group.