(2R,3R,4E)-3-Hydroxy-N-methoxy-N,2-dimethyl-5-phenyl-4-pentenamide | 113453-29-5

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (2R,3R,4E)-3-Hydroxy-N-methoxy-N,2-dimethyl-5-phenyl-4-pentenamide
• 英文别名: (E,2R,3S)-3-hydroxy-N-methoxy-N,2-dimethyl-5-phenylpent-4-enamide
• CAS: 113453-29-5；138694-17-4
• 化学式: C₁₄H₁₉NO₃
• 分子量: 249.31
• InChiKey: PSOYPMWROMNWHJ-FCSPZMLESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  49.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3R,4E)-3-Hydroxy-N-methoxy-N,2-dimethyl-5-phenyl-4-pentenamide 在 Lindlar's catalyst 吡啶 、 咪唑 、 喹啉 、 lithium hydroxide 、 sodium periodate 、 四氧化锇 、 正丁基锂 、 zinc(II) tetrahydroborate 、 草酰氯 、 Proton Sponge 、 ammonium cerium(IV) nitrate 、 四丁基氟化铵 、 氢气 、 三甲基铝 、 双(2-氧代-3-恶唑烷基)次磷酰氯 、 四氯化钛 、 sodium hydride 、 二异丁基氢化铝 、 碳酸氢钠 、 戴斯-马丁氧化剂 、 二甲基亚砜 、 N-甲基吗啉氧化物 、 三乙胺 、 N,N-二异丙基乙胺 、 三氟乙酸 、 环己烯 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 、 甲苯 、 乙腈 为溶剂， 反应 173.47h， 生成 [(2R,3S,6S,7R,8E,11S,12Z,14E)-2,5,6-三甲氧基-3,7,9,11,15-五甲基-16,20,22-三氧代-17-氮杂双环[16.3.1]二十二-1(21),8,12,14,18-五烯-10-基]氨基甲酸酯
  参考文献：
  名称：

  Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin

  摘要：

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.

  DOI：

  10.1021/jo00054a035
• 作为产物：
  描述：

  反式肉桂醛 在 三氟甲磺酸二丁硼 、 三甲基铝 、 三乙胺 作用下， 反应 3.5h， 生成 (2R,3R,4E)-3-Hydroxy-N-methoxy-N,2-dimethyl-5-phenyl-4-pentenamide
  参考文献：
  名称：

  Enantioselective Synthesis of (+)-Crocacin C. An Example of a Highly Challenging Mismatched Double Asymmetric δ-Stannylcrotylboration Reaction

  摘要：

  A concise, enantioselective synthesis of (+)-crocacin C is described, featuring a highly diastereoselective mismatched double asymmetric delta-stannylcrotylboration of the stereochemically demanding chiral aldehyde 9 with the bifunctional crotylborane reagent (S)-E-10. The total synthesis of (+)-crocacin C was accomplished in seven steps (longest linear sequence) starting from commercially available precursors.

  DOI：

  10.1021/ol300476f

文献信息

• Total Synthesis of Aflastatin A
  作者：David A. Evans、Jason J. Beiger、Jason D. Burch、Peter H. Fuller、Frank Glorius、Egmont Kattnig、David A. Thaisrivongs、William C. Trenkle、Joseph M. Young、Jing Zhang

  DOI：10.1021/jacs.2c08244

  日期：2022.11.2

  reaction. Careful comparison of the spectroscopic data for the synthetic C3–C48 degradation fragment to that reported by the isolation group revealed a structural misassignment in the lactol region of the naturally derived degradation product. Ultimately, the data reported for the naturally derived aflastatin A C3–C48 degradation lactol (6a, R = H) were attributed to its derivative lactol trideuteriomethyl

  已经完成了黄曲霉毒素A及其C3-C48降解片段（6a，R=H）的全合成。该合成具有几个复杂的非对映选择性片段偶联，包括 Felkin 选择性三苯甲基催化的 Mukaiyama 醛醇反应、螯合物控制的醛醇反应，涉及与镁的软烯醇化，以及抗 Felkin 选择性硼介导的氧化醛醇反应。将合成 C3-C48 降解片段的光谱数据与分离组报告的光谱数据进行仔细比较，揭示了天然衍生降解产物的乳醇区域的结构错误分配。最终，天然来源的黄曲霉毒素 A C3–C48 降解内酯的数据报告 ( 6a, R = H) 归因于它的衍生物 lactol trideuteriomethyl ether ( 6c , R = CD 3 )。此外，确认了六个立体异构中心（C8、C9 和 C28–C31）的修订绝对配置。
• Asymmetric synthesis of macbecin I
  作者：David A. Evans、Scott J. Miller、Michael D. Ennis、Paul L. Ornstein

  DOI：10.1021/jo00030a006

  日期：1992.2

  The asymmetric synthesis of macbecin I is described wherein the absolute stereochemical relationships were established through the use of chiral boron aldol bond constructions and internally directed alpha-methoxy ketone reduction, while the E,Z dienic amide moiety was installed in one step using a vinylogous phosphonate reagent.
• Total Synthesis of (+)-Crocacin C
  作者：Luiz C. Dias、Luciana G. de Oliveira

  DOI：10.1021/ol016845c

  日期：2001.11.1

  [GRAPHICS]The total synthesis of (+)-crocacin C is described. The convergent asymmetric synthesis relies on the use of a regio- and diastereoselective epoxidation of an allylic alcohol with m-CPBA followed by epoxide opening with Me2CuCNLi2 and a Stille cross-coupling between E-vinyl stannane 5 and E-vinyl iodide 6 to establish the (E,E)-dienamide moiety.
• Enantioselective Synthesis of (+)-Crocacin C. An Example of a Highly Challenging Mismatched Double Asymmetric δ-Stannylcrotylboration Reaction
  作者：Ming Chen、William R. Roush

  DOI：10.1021/ol300476f

  日期：2012.4.6

  A concise, enantioselective synthesis of (+)-crocacin C is described, featuring a highly diastereoselective mismatched double asymmetric delta-stannylcrotylboration of the stereochemically demanding chiral aldehyde 9 with the bifunctional crotylborane reagent (S)-E-10. The total synthesis of (+)-crocacin C was accomplished in seven steps (longest linear sequence) starting from commercially available precursors.
• Asymmetric synthesis of the benzoquinoid ansamycin antitumor antibiotics: total synthesis of (+)-macbecin
  作者：David A. Evans、Scott J. Miller、Michael D. Ennis

  DOI：10.1021/jo00054a035

  日期：1993.1

  A convergent asymmetric synthesis of the antitumor antibiotic macbecin I has been achieved. Six of the seven stereogenic centers within the target structure were controlled using asymmetric aldol methodology, while the final stereogenic center was established through internal asymmetric induction. Fragment coupling was accomplished using a mild, titanium tetrachloride mediated aldol reaction. The C1-C5 unsaturated dienic ester was stereoselectively incorporated through a kinetically controlled Horner-Emmons olefination. Macrolactamization and subsequent refunctionalization afforded macbecin I.