3-(1-Benzenesulfonyl-but-3-enyl)-2-methyl-cyclopent-2-enone | 138606-92-5

• 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: 3-(1-Benzenesulfonyl-but-3-enyl)-2-methyl-cyclopent-2-enone
• 英文别名: 3-[1-(Benzenesulfonyl)but-3-enyl]-2-methylcyclopent-2-en-1-one
• CAS: 138606-92-5
• 化学式: C₁₆H₁₈O₃S
• 分子量: 290.383
• InChiKey: OQLUFKUXCKKPRU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  59.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-甲基-2,4-戊烷二酮 在 sodium methylate 、 sodium hydride 作用下， 反应 32.5h， 生成 3-(1-Benzenesulfonyl-but-3-enyl)-2-methyl-cyclopent-2-enone
  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

文献信息

• Alkylation reactions of 3-(phenylsulfonyl)methyl substituted cyclopentenones
  作者：Albert Padwa、Cheryl L. Muller、Augusto Rodriguez、Scott H. Watterson

  DOI：10.1016/s0040-4020(98)00522-5

  日期：1998.8

  The readily available 2,3-dibromo-1-(phenylsulfonyl)-1-propene (DBP) undergoes facile reaction with several 1,3-dicarbonyl compounds under basic conditions to give (phenylsulfonyl)methyl substituted cyclopentenones. The pendant sulfonyl group at the C3 position of the cyclopentenone ring offers a versatile site for further elaboration via alkylation. These cyclic α-enone systems are easily metallated

  容易获得的2，3-二溴-1-（苯磺酰基）-1-丙烯（DBP）在碱性条件下与几种1,3-二羰基化合物进行容易的反应，得到（苯磺酰基）甲基取代的环戊烯酮。环戊烯酮环的C 3位的磺酰基侧基提供了一个多功能的位点，可通过烷基化进一步进行修饰。这些环状α-烯酮体系很容易用氢化钠金属化，生成的碳负离子会经历双分子和分子内烷基化反应。整个序列为官能化的环戊烯酮提供了简单有效的途径。烷基化砜很容易在与三正加热脱磺酰Ñ-丁基氢化锡和AIBN的甲苯溶液，温度为110°C。使用3-（苯磺酰基）甲基-2-（4-碘丁基）环戊烯酮观察到新的碱基诱导的转化。在HMPA存在下用一当量的NaH处理该化合物，得到4-亚甲基-螺[4.4] non-2-en-1-one。该反应通过最初的γ-烷基化，随后的1,3-氢转移和随后的亚磺酸根阴离子的1,4-消除而进行。