2-烯丙基-1-氧代-1,2,3,4-四氢-2-萘甲酸乙酯 | 251095-18-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: 2-烯丙基-1-氧代-1,2,3,4-四氢-2-萘甲酸乙酯
• 英文名称: ethyl 2-allyl-1-oxo-1,2,3,4-tetrahydro-2-naphthalenecarboxylate
• 英文别名: ethyl 1-oxo-2-prop-2-enyl-3,4-dihydronaphthalene-2-carboxylate
• CAS: 251095-18-8
• 化学式: C₁₆H₁₈O₃
• 分子量: 258.317
• InChiKey: PLNUSYJQQWRZOX-UHFFFAOYSA-N

物化性质

• 沸点：
  362.0±31.0 °C(Predicted)
• 密度：
  1.101±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-烯丙基-1-氧代-1,2,3,4-四氢-2-萘甲酸乙酯 在 碘 作用下， 以 氯仿 为溶剂， 以85%的产率得到5-(iodomethyl)-3',4,4',5-tetrahydro-1'H-spiro[furan-3,2'-naphthalene]-1',2-dione
  参考文献：
  名称：

  由 n 成员环烷酮轻松合成 (n+3) 和 (n+4) 环扩大内酯以及螺酮内酯

  摘要：

  ：我们报告了从简单的 1-烯丙基-2-氧代环烷羧酸乙酯轻松合成功能化 8-、9-、10-、11-和 15 元环内酯的详细研究，这是由三原子环扩大产生的。类似地，实现了 5 至 9 和 6 至 10 元环内酯的四原子环扩大。具有高价碘的烷氧基自由基断裂（ARF）被用作这些环扩展的关键步骤。环扩大通过不稳定的半缩酮中间体进行，在某些情况下是可分离的。在未分离半缩酮的情况下，分子模型计算与羟基酮与半缩酮的相对稳定性一致。在与碘或溴反应时，相同的底物可以转移到离子途径中以提供螺内酯。

  DOI：

  10.1055/s-2007-990820
• 作为产物：
  描述：

  乙酸烯丙酯 、 1-氧代-1,2,3,4-四氢萘-2-羧酸乙酯 在 四(三苯基膦)钯 potassium carbonate 、 Triton X-100 作用下， 以 水 为溶剂， 反应 0.08h， 以92%的产率得到2-烯丙基-1-氧代-1,2,3,4-四氢-2-萘甲酸乙酯
  参考文献：
  名称：

  使用胶体分散系统显着提高水中钯催化的烯丙基烷基化速率

  摘要：

  在中性表面活性剂Triton X-100在水中形成的胶体分散体系中，钯催化的烯丙基烷基化速率大大提高。

  DOI：

  10.1016/s0040-4039(00)01027-3

文献信息

• Palladium-Catalyzed Decarboxylative Asymmetric Allylic Alkylation of β-ketoesters: An Unusual Counterion Effect
  作者：Barry M. Trost、Benjamin Schäffner、Maksim Osipov、Donna A. A. Wilton

  DOI：10.1002/anie.201007803

  日期：2011.4.4

  allyl chloroformate and their β‐ketoesters by using the same catalyst system (see scheme; dba=dibenzylideneacetone, 1,2‐DCE=1,2‐dichloroethane, THF=tetrahydrofuran). The details of this remarkable effect were investigated by performing scavenging experiments and a variety of substrates were successfully used in the procedure.

  买一送一：在相同的催化剂体系下，氯甲酸烯丙酯及其β-酮酸酯可以通过一锅法获得四氢萘酮和茚满酮衍生物的对映异构体（请参阅方案； dba =二苄叉基丙酮，1,2-DCE = 1,2-二氯乙烷，THF =四氢呋喃）。通过执行清除实验研究了这种显着效果的细节，并成功地在该过程中使用了多种基材。
• Enantioselective Alkylation of β-Keto Esters by Phase-Transfer Catalysis Using Chiral Quaternary Ammonium Salts
  作者：Eun Joo Park、Mi Hee Kim、Dae Young Kim

  DOI：10.1021/jo0401772

  日期：2004.10.1

  Catalytic enantioselective alkylation promoted by a quaternary ammonium salt from cinchonine as a phase transfer catalyst is described. Treatment of cyclo β-keto esters with alkyl halide under mild reaction conditions afforded the corresponding α-alkylated β-keto esters in moderate to excellent yields with high enantiomeric excesses

  描述了由辛可宁作为相转移催化剂的季铵盐促进的催化对映选择性烷基化。在温和的反应条件下用烷基卤处理环β-酮酯，得到相应的α-烷基化的β-酮酯，产率中等至优异，对映体过量很高
• Radical Chain Reactions of α-Azido-β-keto Esters with Tributyltin Hydride. A Novel Entry to Amides and Lactams through Regiospecific Nitrogen Insertion
  作者：Luisa Benati、Daniele Nanni、Corrado Sangiorgi、Piero Spagnolo

  DOI：10.1021/jo990837g

  日期：1999.10.1

  A variety of acyclic and carbocyclic alpha-azido-beta-keto esters have been readily prepared from the parent dicarbonyl compounds, and their radical chain reactions with tributyltin hydride have been investigated. These reactions normally result in efficient production of alkoxycarbonyl-substituted amides and lactams and thence provide a new, useful method for regiospecific nitrogen insertion of keto ester compounds. The likely mechanism entails initial addition of tributylstannyl radical to the azido moiety to give a stannylaminyl radical, which readily undergoes intramolecular three-membered cyclization onto the ketone group to form an alkoxyl radical. The alkoxyl radical then undergoes regiospecific beta-scissian to form a stable ring-opened radical that is eventually reduced by tributyltin hydride to propagate the chain. With certain substrates, concomitant deazidation occurs to an important extent. This process, which is unusually observed in radical reactions of alkyl azides, is ascribed to addition of the stannyl radical to the terminal azido nitrogen; subsequent fragmentation of the ensuing 1,3-triazenyl adduct gives stannyl azide and a deazidated alkyl radical, resonance-stabilized by the adjacent carbonyl groups. The radical reactions of 2-azido-2-(ethoxy-carbonyl)-1-tetralone with allyltributylstannane and allyltriphenylstannane have also been investigated with the (missed) aim to achieve nitrogen insertion and concomitant allylation.
• Remarkable rate enhancement of palladium-catalyzed allylic alkylation in water using a colloidal dispersion system
  作者：Shū Kobayashi、William W.-L Lam、Kei Manabe

  DOI：10.1016/s0040-4039(00)01027-3

  日期：2000.8

  The rate of palladium-catalyzed allylic alkylation was dramatically enhanced in a colloidal dispersion system created by a neutral surfactant, Triton X-100, in water.

  在中性表面活性剂Triton X-100在水中形成的胶体分散体系中，钯催化的烯丙基烷基化速率大大提高。
• A Facile Synthesis of (n+3) and (n+4) Ring-Enlarged Lactones as well as of Spiroketolactones from n-Membered Cycloalkanones
  作者：Alfred Hassner、Tarun Pradhan

  DOI：10.1055/s-2007-990820

  日期：2007.11

  simple ethyl l-allyl-2-oxocycloalkanecarboxylates, resulting from a three-atom ring enlargement. Similarly, four-atom ring enlargements of a 5- to 9- and 6- to 10-membered-ring lactones were achieved. Alkoxy radical fragmentation (ARF) with hypervalent iodine was used as the key step for these ring expansions. The ring enlargement proceeds via an unstable hemiketal intermediate, which was isolable in some

  ：我们报告了从简单的 1-烯丙基-2-氧代环烷羧酸乙酯轻松合成功能化 8-、9-、10-、11-和 15 元环内酯的详细研究，这是由三原子环扩大产生的。类似地，实现了 5 至 9 和 6 至 10 元环内酯的四原子环扩大。具有高价碘的烷氧基自由基断裂（ARF）被用作这些环扩展的关键步骤。环扩大通过不稳定的半缩酮中间体进行，在某些情况下是可分离的。在未分离半缩酮的情况下，分子模型计算与羟基酮与半缩酮的相对稳定性一致。在与碘或溴反应时，相同的底物可以转移到离子途径中以提供螺内酯。