4-(Bromomethyl)-5-(phenylsulfonyl)-4-penten-2-one | 128497-04-1

• 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: 4-(Bromomethyl)-5-(phenylsulfonyl)-4-penten-2-one
• 英文别名: (Z)-5-(benzenesulfonyl)-4-(bromomethyl)pent-4-en-2-one
• CAS: 128497-04-1
• 化学式: C₁₂H₁₃BrO₃S
• 分子量: 317.203
• InChiKey: FGSVWHNBIMUIQV-LUAWRHEFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  4-(Bromomethyl)-5-(phenylsulfonyl)-4-penten-2-one 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 以67%的产率得到2-甲基-4-[(苯基磺酰基)甲基]呋喃
  参考文献：
  名称：

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes as versatile reagents for the synthesis of annulated furans and cyclopentenones

  摘要：

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes (DBP and DIP) are conveniently prepared by treating 1-(phenylsulfonyl)-1,2-propadiene with the appropriate halogen. These novel reagents undergo reaction with a variety of simple beta-dicarbonyl anions to give substituted and annulated furans. When the reaction is carried out in polar solvents, 2,3,4-trisubstituted furans are formed. The reaction proceeds by an initial addition-elimination of the carbanion onto the vinyl carbon of the unsaturated sulfone which is followed by intramolecular ring closure on the enolate oxygen atom. When sodium methoxide is used as the base, the initially produced adduct undergoes deacylation and subsequent cyclization to give a 2,4-disubstituted furan. The synthetic utility of the method is demonstrated by a synthesis of (R)-menthofuran. Treatment of DIP with various trimethylsilyl enol ethers in the presence of silver tetrafluoroborate give alkylation products derived from S(N)2 displacement of the terminal halide. These compounds readily cyclize with base to produce an isomeric set of furans. Anions derived from 1,3-dicarbonyls substituted in the C-2 position are found to induce a complete reversal in the mode of ring closure. The major products obtained are 3-[(phenylsulfonyl)methyl]-substituted cyclopentenones. The internal displacement reaction leading to the furan ring apparently encounters an unfavorable A1,3-interaction in the transition state when a substituent group is present at the 2-position of the dicarbonyl compound. This steric interaction is not present in the transition state leading to the cyclopentenone ring. An efficient synthesis of cis-jasmone was carried out using this methodology.

  DOI：

  10.1021/jo00030a025
• 作为产物：
  描述：

  3-Acetyl-4-(bromomethyl)-5-(phenylsulfonyl)-4-penten-2-one 在 sodium methylate 作用下， 以 甲醇 为溶剂， 反应 5.0h， 生成 4-(Bromomethyl)-5-(phenylsulfonyl)-4-penten-2-one
  参考文献：
  名称：

  Use of 2,3-dibromo-1-(phenylsulfonyl)-1-propene as a reagent for the synthesis of annulated furans

  摘要：

  DOI：

  10.1021/jo00301a006

文献信息

• Use of 2,3-dibromo-1-(phenylsulfonyl)-1-propene as a reagent for the synthesis of annulated furans
  作者：Albert Padwa、S. Shaun Murphree、Philip E. Yeske

  DOI：10.1021/jo00301a006

  日期：1990.7
• PADWA, ALBERT;MURPHREE, S. SHAUN;YESKE, PHILIP E., J. ORG. CHEM., 55,(1990) N4, C. 4241-4242
  作者：PADWA, ALBERT、MURPHREE, S. SHAUN、YESKE, PHILIP E.

  DOI：——

  日期：——
• 2,3-Dihalo-1-(phenylsulfonyl)-1-propenes as versatile reagents for the synthesis of annulated furans and cyclopentenones
  作者：Albert Padwa、Masaru Ishida、Cheryl L. Muller、S. Shaun Murphree

  DOI：10.1021/jo00030a025

  日期：1992.2

  2,3-Dihalo-1-(phenylsulfonyl)-1-propenes (DBP and DIP) are conveniently prepared by treating 1-(phenylsulfonyl)-1,2-propadiene with the appropriate halogen. These novel reagents undergo reaction with a variety of simple beta-dicarbonyl anions to give substituted and annulated furans. When the reaction is carried out in polar solvents, 2,3,4-trisubstituted furans are formed. The reaction proceeds by an initial addition-elimination of the carbanion onto the vinyl carbon of the unsaturated sulfone which is followed by intramolecular ring closure on the enolate oxygen atom. When sodium methoxide is used as the base, the initially produced adduct undergoes deacylation and subsequent cyclization to give a 2,4-disubstituted furan. The synthetic utility of the method is demonstrated by a synthesis of (R)-menthofuran. Treatment of DIP with various trimethylsilyl enol ethers in the presence of silver tetrafluoroborate give alkylation products derived from S(N)2 displacement of the terminal halide. These compounds readily cyclize with base to produce an isomeric set of furans. Anions derived from 1,3-dicarbonyls substituted in the C-2 position are found to induce a complete reversal in the mode of ring closure. The major products obtained are 3-[(phenylsulfonyl)methyl]-substituted cyclopentenones. The internal displacement reaction leading to the furan ring apparently encounters an unfavorable A1,3-interaction in the transition state when a substituent group is present at the 2-position of the dicarbonyl compound. This steric interaction is not present in the transition state leading to the cyclopentenone ring. An efficient synthesis of cis-jasmone was carried out using this methodology.