(E)-(1-benzosuberanylidenyl)acetic acid ethyl ester | 53264-14-5

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: (E)-(1-benzosuberanylidenyl)acetic acid ethyl ester
• 英文别名: (E)-ethyl 2-(6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-ylidene)acetate；ethyl (E)-2-(6,7,8,9-tetrahydro-5H-benzo[7]annulen-5-ylidene)acetate；Aethyl-trans-1,2-benzo-3-cycloheptylidenacetat；ethyl (6,7,8,9-tetrahydro-5-benzocycloheptenylidene)acetate；ethyl (2E)-2-(6,7,8,9-tetrahydrobenzo[7]annulen-5-ylidene)acetate
• CAS: 53264-14-5
• 化学式: C₁₅H₁₈O₂
• 分子量: 230.307
• InChiKey: BEDDWIHJBUPEGX-ACCUITESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.6
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 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：

  (E)-(1-benzosuberanylidenyl)acetic acid ethyl ester 在 4-碘甲苯 、 Olah′s reagent 、 triethylamine tris(hydrogen fluoride) 、 间氯过氧苯甲酸 作用下， 以 氯仿 为溶剂， 以87 %的产率得到ethyl 6,6-difluoro-5,6,7,8,9,10-hexahydrobenzo[8]annulene-5-carboxylate
  参考文献：
  名称：

  Catalytic Ring Expanding Difluorination: An Enantioselective Platform to Access β,β‐Difluorinated Carbocycles

  摘要：

  Cyclic β,β‐difluoro‐carbonyl compounds have a venerable history as drug discovery leads, but limitations in the synthesis arsenal continue to impede chemical space exploration. This challenge is particularly acute in the arena of fluorinated medium rings where installing the difluoromethylene unit subtly alters the ring conformation by expanding the internal angle (∠C−CF2−C>∠C−CH2−C): this provides a handle to modulate physicochemistry (e.g. pKa). To reconcile this disparity, a highly modular ring expansion has been devised that leverages simple α,β‐unsaturated esters and amides, and processes them to one‐carbon homologated rings with concomitant geminal difluorination (6 to 10 membered rings, up to 95 % yield). This process is a rare example of the formal difluorination of an internal alkene and is enabled by sequential I(III)‐enabled O‐activation. Validation of enantioselective catalysis in the generation of unprecedented medium ring scaffolds is reported (up to 93 : 7 e.r.) together with X‐ray structural analyses and product derivatization.

  DOI：

  10.1002/anie.202403957
• 作为产物：
  描述：

  1-苯并环庚酮 在 甲酸 、 锌 作用下， 以 苯 为溶剂， 反应 2.0h， 生成 (E)-(1-benzosuberanylidenyl)acetic acid ethyl ester
  参考文献：
  名称：

  乙氧基乙炔基甲醇-αβ-不饱和酯转化：伴随二氧化硒氧化的立体异构

  摘要：

  Benzsuberone与乙氧基乙炔基溴化镁反应生成1-乙氧基乙炔基-1-羟基-2,3-苯并环庚烯，与弱酸（二氧化碳）重排后，生成顺式-1,2-苯并3-苯并-3-环庚烯基乙酸乙酯（4，R ′＝ CO 2 Et，R 1＝ H）和相应的反式化合物。使用二氧化硒时，两种酯均会产生相同的γ-内酯，

  DOI：

  10.1016/s0040-4020(01)97022-x

文献信息

• Facile access to chiral 4-substituted chromanes through Rh-catalyzed asymmetric hydrogenation
  作者：Lin Tao、Qingyang Zhao、Xumu Zhang、Xiu-Qin Dong

  DOI：10.1016/j.cclet.2020.01.001

  日期：2020.7

  Rh/ZhaoPhos-catalyzed asymmetric hydrogenation of a series of (E)-2-(chroman-4-ylidene)acetates was successfully developed to prepare various chiral 4-substituted chromanes with high yields and excellent enantioselectivities (up to 99% yield, 98% ee). Moreover, the gram-scale hydrogenation could be performed well in the presence of 0.02 mol% catalyst loading (TON = 5000), the hydrogenation product was easily

  摘要成功开发了Rh / ZhaoPhos催化的一系列（E）-2-（chroman-4-yylne）乙酸酯的不对称氢化反应，以高收率和优异的对映选择性（高达99％的收率， 98％ee）。此外，在催化剂用量为0.02 mol％（TON = 5000）的情况下，克级加氢反应可以很好地进行，加氢产物很容易转化成其他重要的化合物，这证明了这种不对称催化方法的合成实用性。
• Design and synthesis of conformationally constrained analogues of cis-cinnamic acid and evaluation of their plant growth inhibitory activity
  作者：Keisuke Nishikawa、Hiroshi Fukuda、Masato Abe、Kazunari Nakanishi、Yuta Tazawa、Chihiro Yamaguchi、Syuntaro Hiradate、Yoshiharu Fujii、Katsuhiro Okuda、Mitsuru Shindo

  DOI：10.1016/j.phytochem.2013.10.001

  日期：2013.12

  conformationally constrained cis-CA analogues, in which the aromatic ring and cis-olefin were connected by a carbon bridge, were designed, synthesized, and evaluated as plant growth inhibitors. The results of the present study demonstrated that the inhibitory activities of the five-membered and six-membered bridged compounds were enhanced, up to 0.27 μM, and were ten times higher than cis-CA, while the potency

  1-O-顺式-肉桂酰-β-D-吡喃葡萄糖被认为是最有效的化感化学候选物之一，由 Hiradate 等人从 Spiraea thunbergii Sieb 中分离出来。 (2004)，他认为它的强抑制活性来自顺式肉桂酸，这对于植物毒性至关重要。在本研究中，研究了顺式肉桂酸（cis-CA）的关键结构特征和取代基对生菜根生长抑制的影响。这些结构-活性关系研究表明了芳环和羧酸部分的空间关系的重要性。在此背景下，设计、合成了构象受限的顺式-CA类似物，其中芳环和顺式烯烃通过碳桥连接，并作为植物生长抑制剂进行了评估。本研究结果表明，五元和六元桥化合物的抑制活性增强，高达0.27 μM，比cis-CA高十倍，而其他化合物的抑制活性有所降低。
• Heteroleptic Copper-Based Complexes for Energy-Transfer Processes: <i>E</i> → <i>Z</i> Isomerization and Tandem Photocatalytic Sequences
  作者：Corentin Cruché、William Neiderer、Shawn K. Collins

  DOI：10.1021/acscatal.1c01983

  日期：2021.7.16

  Energy-transfer processes involving copper complexes are rare. Using an optimized heteroleptic copper complex, Cu(bphen)(XantPhos)BF4, photosensitized E → Z isomerization of olefins is demonstrated. The XantPhos ligand afforded sensitizers with improved catalyst stability, while the bphen ligand lengthened the excited-state lifetime. A series of 25 di- and trisubstituted alkenes underwent photoisomerization

  涉及铜配合物的能量转移过程很少见。使用优化的杂配铜配合物 Cu( bphen )( XaNTPhOS )BF 4，证明了烯烃的光敏E → Z异构化。所述XANTPHOS配体，得到具有改善的催化剂稳定性的增感剂，同时将BPhen配体延长了激发态寿命。一系列 25 个二取代和三取代烯烃经历了光异构化，包括大环和 1,3-烯炔。Cu( bphen )( XaNTPhOS )BF 4 也可以在使用芳基磺酰氯的串联 ATRA/光异构化过程中使用，这是使用卤化物取代的烯烃进行光异构化的一个例子。
• Plant growth regulator compounds
  申请人：SYNGENTA PARTICIPATIONS AG

  公开号：US11136292B2

  公开（公告）日：2021-10-05

  The present invention relates to relates to novel strigolactone derivatives of formula (I), to processes for preparing these derivatives including intermediate compounds, to seeds comprising these derivatives, to plant growth regulator or seed germination promoting compositions comprising these derivatives and to methods of using these derivatives in controlling the growth of plants and/or promoting the germination of seeds.

  本发明涉及式（I）的新型绞股蓝内酯衍生物、制备这些衍生物（包括中间体化合物）的工艺、包含这些衍生物的种子、包含这些衍生物的植物生长调节剂或促进种子萌发的组合物，以及使用这些衍生物控制植物生长和/或促进种子萌发的方法。
• Isomerization processes of electronically excited stilbene and diphenylbutadiene in liquids. Are they one-dimensional?
  作者：Minyung Lee、John N. Haseltine、Amos B. Smith、Robin M. Hochstrasser

  DOI：10.1021/ja00196a004

  日期：1989.7