(R)-2-methyl-2-(2-E-nitrovinyl)-5-pentanolide | 134453-99-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (R)-2-methyl-2-(2-E-nitrovinyl)-5-pentanolide
• 英文别名: (3R)-3-methyl-3-[(E)-2-nitroethenyl]oxan-2-one
• CAS: 134453-99-9
• 化学式: C₈H₁₁NO₄
• 分子量: 185.18
• InChiKey: PVCHJHUFDPSNRD-WTSVBCDHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  13
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.62
• 拓扑面积：
  72.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (R)-2-methyl-2-(2-E-nitrovinyl)-5-pentanolide 在 盐酸 、 对甲苯磺酸 作用下， 反应 72.0h， 生成 (2R)-2-(3'-methoxyphenyl)-2-methyl-5-pentanolide
  参考文献：
  名称：

  Asymmetric Synthesis of (-)-Aphanorphine and (-)-Eptazocine

  摘要：

  Formal asymmetric syntheses of (-)-aphanorphine and (-)-eptazocine were done, utilizing asymmetric nitroolefination reaction of alpha-methyl-delta-valerolactone and a new aromatization of Diels-Alder adducts of chiral nitroolefins with the Danishefsky's diene.

  DOI：

  10.3987/com-95-s88
• 作为产物：
  描述：

  (E)-1-<(S)-2-hydroxymethylpyrrolidin-1-yl>-2-nitroethylene 、 chlorozinc(1+);5-methyl-3,4-dihydro-2H-pyran-6-olate 以 四氢呋喃 为溶剂， 生成 (S)-(-)-2-Methyl-2-(2'-nitrovinyl)-δ-valerolactone 、 (R)-2-methyl-2-(2-E-nitrovinyl)-5-pentanolide
  参考文献：
  名称：

  An improved asymmetric nitroolefination of α-alkyl-γ- and δ-lactones with modified nitroenamines

  摘要：

  New chiral nitroenamines 4a, b were found to be very effective for asymmetric nitroolefination of alpha-alkyl-gamma- and delta-lactones. The enantiomeric excess of the product ran up to 99%. A possible chelation model for the transition state of the asymmetric nitroolefination was discussed.

  DOI：

  10.1016/0040-4039(94)02175-b

文献信息

• A chiral synthesis of a unique secodehydroabietane from tall oil.
  作者：Kaoru FUJI、Shang-Zhen ZHENG、Manabu NODE、Xiao-Jiang HAO

  DOI：10.1248/cpb.39.202

  日期：——

  A total synthesis of naturally occurring (+)-9, 10-secoabieta-8, 11, 13-trien-18, 10-olide (1) has been achieved from a chiral building block, (R)-2-methyl-2-(2-E-nitrovinyl)-5-pentanolide (3).

  由手性结构单元 (R)-2-methyl-2 实现了天然存在的 (+)-9, 10-secoabieta-8, 11, 13-trien-18, 10-olide (1) 的全合成-(2-E-硝基乙烯基)-5-戊内酯(3)。
• An efficient asymmetric synthesis of nitroolefinic lactones with chiral nitroenamines possessing bulky chiral leaving groups
  作者：Xiaowu Yang、Rui Wang

  DOI：10.1016/s0957-4166(97)00452-7

  日期：1997.10

  An efficient asymmetric nitroolefination of enolates 4a-c, 5 afforded multifunctional group nitroolefinic lactones 7a-e and 8a,b containing stereogenic quaternary carbon centers using bulky chiral nitroenamines 1a,b–3a,b as chiral auxiliaries. Studies on the effect of the bulkiness of leaving group showed that bulky nitroenamines 1a,b gave higher ees and yields than those of the less bulky 2a,b–3a

  有效的烯醇盐4a-c，5的不对称硝基烯烃化反应，使用了庞大的手性亚硝胺1a，b-3a，b作为手性助剂，从而得到了多官能团的硝基烯烃内酯7a-e和8a，b，其中含有立体生成的季碳中心。研究的离去基团的体积的效果表明，笨重nitroenamines 1A，B，得到更高EES和产量比那些不太笨重的图2a，2b-3A，3B。提出了一种可能的循环跃迁模型，以阐明S的选择性。
• Enhanced Reactivity of Zinc Enolates over Lithium Enolates in Asymmetric Nitroolefination.
  作者：Kaoru FUJI、Takeo KAWABATA、Yoshimitsu NANIWA、Toshiumi OHMORI、Manabu NODE

  DOI：10.1248/cpb.42.999

  日期：——

  Zinc enolates derived from an ester and a lactone, 1 and 4, were found to have enhanced reactivity over the corresponding lithium enolates in asymmetric nitroolefination.

  研究发现，在不对称硝基油化反应中，由酯和内酯衍生的烯醇化锌 1 和 4 比相应的烯醇化锂具有更强的反应活性。
• An Asymmetric Nitroolefination of α-Alkyl-γ-and δ-Lactones with Modified Nitroenamines
  作者：Kiyoharu Nishide、Ryuichi Kurosaki、Kouichi Hosomi、Hitoshi Imazato、Takehisa Inoue、Manabu Node、Toshiumi Ohmori、Kaoru Fuji

  DOI：10.1016/0040-4020(95)00683-y

  日期：1995.10

  New chiral nitroenamines 4a,b having (S)-2-t-butyldimethylsiloxymethylpyrrolidine as an auxiliary were found to be very effective for asymmetric nitroolefination of alpha-alkyl-gamma- and delta-lactones. The enantiomeric excess of the product increased remarkably in the reaction with gamma-lactones compared with previous nitroenamines 1a,b. A possible chelation model for the transition state of the asymmetric nitroolefination is discussed.
• FUJI, KAORU;ZHENG, SHANG-ZHEN;NODE, MANABU;HAO, XIAO-JIANG, CHEM. AND PHARM. BULL., 39,(1991) N, C. 202-203
  作者：FUJI, KAORU、ZHENG, SHANG-ZHEN、NODE, MANABU、HAO, XIAO-JIANG

  DOI：——

  日期：——