(4E)-4-(2-bromocyclohex-2-en-1-ylidene)-2,2-dimethylbutanoic acid | 214853-70-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (4E)-4-(2-bromocyclohex-2-en-1-ylidene)-2,2-dimethylbutanoic acid
• CAS: 214853-70-0
• 化学式: C₁₂H₁₇BrO₂
• 分子量: 273.17
• InChiKey: ZDWQHXGDDJKQMI-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4E)-4-(2-bromocyclohex-2-en-1-ylidene)-2,2-dimethylbutanoic acid 在 sodium acetate 、 一氯化碘 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 生成 (R)-5-((R)-2-Bromo-3-hydroxy-cyclohex-1-enyl)-3,3-dimethyl-dihydro-furan-2-one
  参考文献：
  名称：

  Regio- and stereoselective oxidative difunctionalization of alkylidene cyclohexenes

  摘要：

  Stereo- and regioselective oxidation of alkylidene cyclohexenes affords novel gamma-lactones, delta-lactones and related structures. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(99)02043-2
• 作为产物：
  描述：

  2-溴-2-环己烯-1-酮 在 cerium(III) chloride 、 乙烯基溴化镁 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 乙醚 、 甲苯 为溶剂， 反应 4.0h， 生成 (4E)-4-(2-bromocyclohex-2-en-1-ylidene)-2,2-dimethylbutanoic acid
  参考文献：
  名称：

  Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis

  摘要：

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.

  DOI：

  10.1021/jo010752r

文献信息

• Intramolecularly competitive Ireland Claisen rearrangements: Stereoselective synthesis of alkylidene cyclohexenes
  作者：Xiaowei Zhang、Matthias C. McIntosh

  DOI：10.1016/s0040-4039(98)01525-1

  日期：1998.9

  Unsymmetrical bis-allyl silylketene acetals derived from cyclohexenones undergo regio- and stereoselective Ireland Claisen rearrangements to afford alkylidene cyclohexenes in good yield.

  衍生自环己烯酮的不对称双烯丙基甲硅烷基乙烯酮缩醛经过区域和立体选择性的爱尔兰克莱森重排，以高收率得到亚烷基环己烯。
• Intramolecularly Competitive Ireland-Claisen Rearrangements:  Scope and Potential Applications to Natural Product Synthesis
  作者：Sang-phyo Hong、Harriet A. Lindsay、Tripura Yaramasu、Xiaowei Zhang、Matthias C. McIntosh

  DOI：10.1021/jo010752r

  日期：2002.4.1

  A variety of bis-allylic esters were prepared by vinylmetal addition to cycloalkenones followed by esterification either in situ or in a separate operation. For chiral cyclohexenones, the vinyl additions generally occurred with > 10:1 diastereoselectivity. Although in some cases the bis-allylic esters proved to be sensitive to silica gel or other adsorbents, all of the esters examined could be isolated in acceptable purity. The Ireland-Claisen rearrangement of the bis-allylic esters occurred with complete regioselectivity via the exocyclic alkene. The alkene stereochemistry and the stereochemistry at C-2 and C-3 of the pentenoic acid products were consistent with a chairlike transition state in the rearrangement. Substituents at the carbons adjacent to the allylic carbinol carbon (i.e., C-2 or C-6 in cyclohexenone-derived substrates) directed the stereochemical course of the rearrangement. The rearrangements generally proceeded so as to place the larger of the C-2 or C-6 substituents in the pseudoequatorial position with respect to the chairlike transition state. For a bis-allylic ester bearing both a C-2-CH3 and a C-6-OMEM substituent, the rearrangement product resulted from the nominally smaller OMEM substituent occupying a pseudoequatorial position with respect to the chairlike transition state.
• Regio- and stereoselective oxidative difunctionalization of alkylidene cyclohexenes
  作者：Sang-Phyo Hong、Matthias C McIntosh、Tosha Barclay、Wally Cordes

  DOI：10.1016/s0040-4039(99)02043-2

  日期：2000.1

  Stereo- and regioselective oxidation of alkylidene cyclohexenes affords novel gamma-lactones, delta-lactones and related structures. (C) 1999 Elsevier Science Ltd. All rights reserved.