ethyl 5-cyclopentylpenta-2,3-dienoate | 942283-74-1

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl 5-cyclopentylpenta-2,3-dienoate
• CAS: 942283-74-1
• 化学式: C₁₂H₁₈O₂
• 分子量: 194.274
• InChiKey: DENUWTZSDLABRH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  ethyl 5-cyclopentylpenta-2,3-dienoate 、 邻苯二甲醛 在 乙基二苯基膦 作用下， 以 甲苯 为溶剂， 以96%的产率得到(E)-ethyl 3-(2-cyclopentylvinyl)-2-naphthoate
  参考文献：
  名称：

  Phosphine-Mediated Iterative Arene Homologation Using Allenes

  摘要：

  A PPh3-mediated multicomponent reaction between o-phthalaldehydes, nucleophiles, and monosubstituted allenes furnishes functionalized non-C-2-symmetric naphthalenes in synthetically useful yields. When the o-phthalaldehydes were reacted with 1,3-disubstituted allenes in the presence of PPh2Et, naphthalene derivatives were also obtained in up to quantitative yields. The mechanism of the latter transformation is straightforward: aldol addition followed by Wittig olefination and dehydration. The mechanism of the former is a tandem gamma-umpolung/aldol/Wittig/dehydration process, as established by preparation of putative reaction intermediates and mass spectrometric analysis. This transformation can be applied iteratively to prepare anthracenes and tetracenes using carboxylic acids as pronucleophiles.

  DOI：

  10.1021/jacs.5b07403
• 作为产物：
  描述：

  3-环戊基丙酸 、 乙氧甲酰基亚甲基三苯基膦 在 草酰氯 、 N,N-二甲基甲酰胺 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 ethyl 5-cyclopentylpenta-2,3-dienoate
  参考文献：
  名称：

  膦催化的不对称串联异构化/烯丙胺与烯丙酸酯的环化：饱和 C-N 键的对映选择性环化

  摘要：

  在手性膦的催化下，实现了烯丙胺与烯丙酸酯的不对称异构化/环化级联反应。广泛的 γ 取代的烯丙酸酯可耐受，以高产率提供手性吡咯啉衍生物，并具有优异的对映选择性。在该反应中，容易获得的N-烯丙胺通过 1,4-质子位移异构化为反应性脂肪族亚胺是一个关键步骤，它避免了高度不稳定的烷基N-磺酰亚胺的分离。

  DOI：

  10.1021/acs.orglett.1c03483

文献信息

• Phosphine-Catalyzed Formation of Carbon−Sulfur Bonds: Catalytic Asymmetric Synthesis of γ-Thioesters
  作者：Jianwei Sun、Gregory C. Fu

  DOI：10.1021/ja101251d

  日期：2010.4.7

  only add to the gamma position of allenoates, overcoming their propensity to add to the beta position in the absence of a catalyst, but do so with very good enantioselectivity. Sulfur nucleophiles are now added to the three families of nucleophiles (carbon, nitrogen, and oxygen) that had earlier been shown to participate in catalyzed gamma additions. The phosphine catalyst of choice, TangPhos, had

  已经开发了一种羰基化合物催化不对称 γ 磺基化的方法。在合适的催化剂存在下，硫醇不仅添加到烯丙酸酯的 γ 位置，克服了它们在没有催化剂的情况下添加到 β 位置的倾向，而且这样做具有非常好的对映选择性。硫亲核试剂现在被添加到三个亲核试剂家族（碳、氮和氧）中，这些亲核试剂早先被证明参与了催化伽马加成。选择的膦催化剂 TangPhos 以前仅用作过渡金属的手性配体，而不是用作有效的对映选择性亲核催化剂。
• Phosphahelicenes in Asymmetric Organocatalysis: [3+2] Cyclizations of γ-Substituted Allenes and Electron-Poor Olefins
  作者：Maxime Gicquel、Yang Zhang、Paul Aillard、Pascal Retailleau、Arnaud Voituriez、Angela Marinetti

  DOI：10.1002/anie.201500299

  日期：2015.4.27

  The first use of phosphahelicene in enantioselective organocatalysis is reported. New chiral phosphahelicenes have been prepared and enable highly enantioselective [3+2] cyclization reactions between arylidene‐ or alkylidenemalononitriles and γ‐substituted allenoates or cyanoallenes. These reactions afford cyclopentene derivatives in both high yields and diastereoselectivities, with enantiomeric excesses

  报道了在非对映选择性的有机催化中首次使用磷烯。已经制备了新的手性磷杂环烯，它们可以使亚芳基或亚烷基烯丙二腈与γ-取代的烯丙酸酯或氰基烯丙烯之间进行高度对映选择性的[3 + 2]环化反应。这些反应以高收率和非对映选择性提供环戊烯衍生物，对映体过量高达97％。
• Synthesis of Substituted Pyrroles via Copper-Catalyzed Cyclization of Ethyl Allenoates with Activated Isocyanides
  作者：Kui Lu、Fang Ding、Long Qin、Xiaoliang Jia、Chuanming Xu、Xia Zhao、Qingwei Yao、Peng Yu

  DOI：10.1002/asia.201600761

  日期：2016.8.5

  new method for the synthesis of di‐ and trisubstituted pyrroles via copper‐catalyzed cyclization of ethyl allenoates with activated isocyanides has been developed. In contrast to related annulation reactions previously reported, this new process features a skeletal rearrangement in which the aryl sulfonyl moiety, which functions as the electron‐withdrawing group in the α‐carbon of the isocyanide, was

  已经开发了一种新的方法，该方法通过铜与活化的异氰酸酯催化的烯丙酸乙酯的铜催化环化反应来合成二取代和三取代的吡咯。与先前报道的相关环空反应相反，该新过程具有骨架重排的特征，其中发现异氰酸酯的α-碳中起吸电子基团作用的芳基磺酰基部分迁移到了C的γ-碳上。最终产品中的起始烯丙基化。
• Small-Molecule Inhibitors of Protein Geranylgeranyltransferase Type I
  作者：Sabrina Castellano、Hannah D. G. Fiji、Sape S. Kinderman、Masaru Watanabe、Pablo de Leon、Fuyuhiko Tamanoi、Ohyun Kwon

  DOI：10.1021/ja070274n

  日期：2007.5.1

  Small molecules that inhibit the geranylgeranylation of K-Ras4B and RhoA by protein geranylgeranyltransferase type I (GGTase-I) were identified from chemical genetic screens of heterocycles synthesized through phosphine catalysis of allenes. To further improve the efficacy of the GGTase-I inhibitors (GGTIs), 4288 related compounds bearing core dihydropyrrole/pyrrolidine and tetrahydropyridine/piperidine scaffolds were synthesized on SynPhase lanterns in a split-pool manner through phosphine-catalyzed [3 + 2] and [4 + 2] annulations of resin-bound allenoates. Testing of the 4288 analogues resulted in several GGTIs exhibiting submicromolar IC50 values. Because proteins such as Ras and Rho GTPases are implicated in oncogenesis and metastasis, these GGTIs might ultimately lead to the development of novel antitumor therapeutics.
• Phosphine-Catalyzed Synthesis of 3,3-Spirocyclopenteneoxindoles from γ-Substituted Allenoates: Systematic Studies and Targeted Applications
  作者：Catherine Gomez、Maxime Gicquel、Jean-Christophe Carry、Laurent Schio、Pascal Retailleau、Arnaud Voituriez、Angela Marinetti

  DOI：10.1021/jo302460d

  日期：2013.2.15

  The phosphine-promoted [3 + 2] cyclizations between gamma-substituted allenoates and arylideneoxindoles have been applied to the stereoselective synthesis of spiro(cyclopentene)oxindoles with trisubstituted cyclopentene units. It has been demonstrated that PPh3 operates a very efficient control of the relative stereochemistry of the three stereogenic centers of the final spiranic products. Focused experiments have been carried out then so as to access carbocyclic analogues of an important series of anticancer agents inhibiting MDM2-p53 interactions.