Phenylsulfonyle-2 heptene-6-oate de methyle | 133124-32-0

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: Phenylsulfonyle-2 heptene-6-oate de methyle
• 英文别名: methyl 2-(phenylsulfonyl)-6-heptenoate；Methyl 2-(benzenesulfonyl)hept-6-enoate
• CAS: 133124-32-0
• 化学式: C₁₄H₁₈O₄S
• 分子量: 282.361
• InChiKey: SJRGVGKXOQOKLE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  Phenylsulfonyle-2 heptene-6-oate de methyle 在 二甲基硫 、 sodium hydride 、 臭氧 作用下， 以 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 15.75h， 生成 1-Ethyl methyl (+/-)-(Z)-7-methyl-7-(phenylsulfonyl)-2-octenedioate
  参考文献：
  名称：

  Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions

  摘要：

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.

  DOI：

  10.1021/jo00077a043
• 作为产物：
  描述：

  5-碘-1-戊烯 、 苯磺酰乙酸甲酯 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 Phenylsulfonyle-2 heptene-6-oate de methyle
  参考文献：
  名称：

  Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions

  摘要：

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.

  DOI：

  10.1021/jo00077a043

文献信息

• Formation de cyclopentanes lors de réactions de Heck
  作者：Guy Fournet、Geneviève Balme、Jacques Gore

  DOI：10.1016/s0040-4020(01)90073-0

  日期：1990.1

  The Heck reaction of alkenes bearing in δ position an enolate of β-diester, βketo ester or β-sulfonyl ester leads to cyclopentanes issued from the intramolecular displacement of the carbone sp3-palladium bond by this enolate. This cyclisation is not observed when the enolate is in β or ε position or in the case of a δ-ethylenic amine and βelimination products are only obtained.

  δ位置的烯烃的Heck反应是β-二酯，β-酮酸酯或β-磺酰基酯的烯醇化物导致的环戊烷是由烯醇sp 3-钯键的分子内位移引起的。当烯醇化物处于β或ε位置或在δ-亚乙基胺的情况下，未观察到这种环化，并且仅获得β消除产物。
• A Second Generation Synthesis of Roseophilin and Chromophore Analogues
  作者：Alois Fürstner、Thomas Gastner、Holger Weintritt

  DOI：10.1021/jo982088t

  日期：1999.4.1

  A concise, flexible, and high-yielding synthesis of the macrocyclic compound 4 is outlined which served as a key intermediate in a previous total synthesis of the antitumor active alkaloid roseophilin 1. The key steps of this approach consist of a Pd(0)-catalyzed reaction of vinyloxirane 6 with sulfone 7 and in a subsequent ring closing metathesis (RCM) reaction for the formation of the 13-membered ring catalyzed by the ruthenium carbene Cl-2(PCy3)(2)Ru=CHCH=CPh2 introduced by Grubbs. Moreover, nitrile ylide cycloaddition reactions are used for the preparation of roseophilin side chain mimics. Finally, the synthesis of various chromophore analogues of 1 is reported, including deschloro-desmethoxyroseophilin 12 which is the most elaborate derivative of this complex target reported so far.
• Carbocyclization Reaction of Active Methine Compounds with Unactivated Alkenyl or Alkynyl Groups Mediated by TiCl₄−Et₃N
  作者：Osamu Kitagawa、Takashi Suzuki、Tadashi Inoue、Yoko Watanabe、Takeo Taguchi

  DOI：10.1021/jo981603k

  日期：1998.12.1

  In the presence of TiCl4, Et3N, and I-2, iodocarbocyclization reaction of various active methine compounds having alkenyl groups gave iodocycloalkane derivatives in good yields. On the other hand, TiCl4 and Et3N promote the carbocyclization of active methine compounds with 4-alkynyl groups in the absence of I-2 to give methylenecyclopentane derivatives in good yields. This reaction proceeds with high streoselectivity through a cis-addition of trichlorotitanium enolates of active methine compounds to alkynes, and the resulting vinyltitanium intermediates can be further functionalized by the reaction with various electrophiles.
• Functionalized carbocycles by tandem dealkoxycarbonylation-Michael addition reactions
  作者：Richard A. Bunce、Eric D. Dowdy、Paul B. Jones、Elizabeth M. Holt

  DOI：10.1021/jo00077a043

  日期：1993.12

  A tandem dealkoxycarbonylation-Michael addition reaction has been developed as a synthetic route to highly functionalized carbocycles. Methyl esters, activated toward decarboxylation by an electron-withdrawing group at C-2 and tethered by a three- or four-carbon chain to an acrylate Michael acceptor, have been prepared and used as the cyclization substrates. Treatment of these compounds with LiCl in HMPA at 120-degrees-C or 4 h results in selective S(N)2 dealkylation of the methyl esters, decarboxylation, and cyclization of the intermediate anions by a Michael addition to the pendant acrylate moiety. This affords 45-90% of the cyclopentane- and cyclohexaneacetic esters substituted at C-2 by an electron-with drawing group. Moderate to excellent selectivity (3:1-99:1) in favor of the product having the electron-withdrawing group trans to the acetic ester side chain is observed. The reaction works best for the preparation of five-membered rings, and cyclizations proceed most cleanly from substrates which cyclize through a tertiary carbanion. Synthetic and mechanistic details as well as optimization studies and product structure proofs are presented.