3-acetyl-2-methyl-5-(4-chlorophenyl)-4,5-dihydrofuran | 134391-04-1

• 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: 3-acetyl-2-methyl-5-(4-chlorophenyl)-4,5-dihydrofuran
• 英文别名: 1-[2-(4-Chlorophenyl)-5-methyl-2,3-dihydrofuran-4-yl]ethanone
• CAS: 134391-04-1
• 化学式: C₁₃H₁₃ClO₂
• 分子量: 236.698
• InChiKey: RWVDJQYMBNKQRD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-acetyl-2-methyl-5-(4-chlorophenyl)-4,5-dihydrofuran 在 ammonium acetate 作用下， 以 二甲基亚砜 为溶剂， 反应 6.0h， 生成 2-(4-chlorophenyl)-4-methyl-2,3-dihydrofuro[3,2-c]pyridine
  参考文献：
  名称：

  [5C + 1N]公告：取代二氢呋喃[3,2- c ]吡啶的两条新颖途径

  摘要：

  描述了两种基于[5C + 1N]环合的新颖路线，用于合成2,3-二氢呋喃[3,2- c ]吡啶。两种途径均使用乙酸铵（NH 4 OAc）作为氨源。第一种方法利用1-酰基-1-[[（二甲基氨基）链烯酰基]环丙烷作为五碳1,5-双亲电子物质，并将环丙基酮的[5C + 1N]环合和区域选择性环扩大结合到一个罐中，而第二种方法利用3-酰基-2-[（（二甲氨基）烯基] -4,5-二氢呋喃作为五碳合成子，其涉及顺序的分子间氮杂加成，分子内氮杂亲核加成/消除和脱水反应。

  DOI：

  10.1021/ol302314c
• 作为产物：
  描述：

  1,1-Diacetyl-2-(p-chlorphenyl)cyclopropan 在 三乙烯二胺 作用下， 以 二甲基亚砜 为溶剂， 以87%的产率得到3-acetyl-2-methyl-5-(4-chlorophenyl)-4,5-dihydrofuran
  参考文献：
  名称：

  有机催化的克-威尔逊重排：DABCO催化的环丙基酮扩环成2,3-二氢呋喃

  摘要：

  利用均轭共轭加成工艺开发了环丙基酮对2，3-二氢呋喃的有机催化Cloke-Wilson重排。以1,4-二氮杂双环[2.2.2]辛烷为催化剂，在DMSO中于120°C进行的重排通常以高收率，唯一的区域选择性和较宽的底物范围进行。该机构包括立体化学分析和中间隔离支撑一个S的检查Ñ机制的1型环开口。

  DOI：

  10.1021/acs.orglett.7b00805

文献信息

• Domino [3+3] Annulation/Ring-Cleavage Reactions of 1,3-Bis(trimethylsilyloxy)-1,3-butadienes with 5-Aryl- and 5-Vinyl-3-acyl- 4,5-dihydrofurans: Efficient Synthesis of 5-(4-Chlorobut-2-en-1-yl)- and 5-(2-Aryl-2-chloroethyl)salicylates
  作者：Matthias Lau、Muhammad Sher、Alexander Villinger、Christine Fischer、Peter Langer

  DOI：10.1002/ejoc.201000158

  日期：2010.7

  The domino “[3+3] cyclization–ring-opening” reactions of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 3-acetyl-5-vinyl-4,5-dihydrofurans afforded 5-(4-halobut-2-en-1-yl)salicylates. The reactions of 1,3-bis(trimethylsilyloxy)-1,3-butadienes with 3-acetyl-5-aryl-4,5-dihydrofurans gave 5-(2-aryl-2-chloroethyl)salicylates.

  1,3-双(三甲基甲硅烷氧基)-1,3-丁二烯与3-乙酰-5-乙烯基-4,5-二氢呋喃的多米诺“[3+3]环化-开环”反应得到5-(4- halobut-2-en-1-yl) 水杨酸盐。1,3-双(三甲基甲硅烷氧基)-1,3-丁二烯与3-乙酰基-5-芳基-4,5-二氢呋喃的反应得到5-(2-芳基-2-氯乙基)水杨酸酯。
• Non-decarbonylative photochemical versus thermal activation of Bu₄N[Fe(CO)₃(NO)] – the Fe-catalyzed Cloke–Wilson rearrangement of vinyl and arylcyclopropanes
  作者：Che-Hung Lin、Dominik Pursley、Johannes E. M. N. Klein、Johannes Teske、Jennifer A. Allen、Fabian Rami、Andreas Köhn、Bernd Plietker

  DOI：10.1039/c5sc02342d

  日期：——

  The base metal complex Bu4N[Fe(CO)3(NO)] (TBA[Fe]) catalyzes the rearrangement of vinyl and arylcyclopropanes both under thermal or photochemical conditions to give the corresponding vinyl or aryldihydrofuranes in good to excellent...

  贱金属配合物 Bu4N[Fe(CO)3(NO)] (TBA[Fe]) 在热或光化学条件下催化乙烯基和芳基环丙烷的重排，以良好至优异的性能生成相应的乙烯基或芳基二氢呋喃。
• Electronic and steric effects in the addition of electrophilic 1,3-dicarbonylalkyl radicals to styrenes
  作者：Enrico Baciocchi、Renzo Ruzziconi

  DOI：10.1021/jo00015a037

  日期：1991.7

  The addition reactions of 1,3-dicarbonylalkyl radicals to ring-substituted styrenes have been kinetically investigated in MeOH and/or MeCN. It has been observed that the rate effect of ring substituents is nearly identical in the reactions of MeCOCHCOMe (1), MeOCOCHCOMe (2) and MeOCOCHCOOMe (4), the rho-value, in MeOH being -0.96, -1.01 and -1.06, respectively. Since the three radicals are relatively strong oxidants and have similar reduction potentials, an important contribution of the charge transfer structure RCOCHCORCH2CHAr.+ to the addition transition state is suggested. It has also be found that in the reactions of 1 and 4 with alpha-alkyl-substituted styrenes the rate of addition is strongly influenced by the nature of the alkyl group, decreasing in the order: Me > Et > (i)Pr > (t)Bu. The observed effects are much larger than those reported for the corresponding reactions of the nucleophilic cyclohexyl radical. It is suggested that the alpha-alkyl substituents exert an effect of steric inhibition of resonance thereby ring delocalization of the charge and/or unpaired electron in the transition state is significantly reduced. Delocalization may be more important in the reactions of 1 and 4 than in those of the cyclohexyl radical since it is possible that the former utilizes a transition state occurring later along the reaction coordinate and/or characterized by a larger extent of charge transfer.
• Synthesis of 5-(2-aryl-2-haloethyl)salicylates by the first domino ‘[3+3] cyclization/ring-cleavage’ reactions of 1,3-bis(silyloxy)-1,3-butadienes with 3-acetyl-5-aryl-4,5-dihydrofurans
  作者：Matthias Lau、Peter Langer

  DOI：10.1016/j.tetlet.2008.07.049

  日期：2008.9

  5-(2-Aryl-2-haloethyl)salicylates are efficiently prepared by the first domino '[3+3] cyclization/ring-cleavage' reactions of 1,3-bis(silyloxy)-1,3-butadienes with 3-acetyl-5-aryl,5-dihydrofurans. (C) 2008 Elsevier Ltd. All rights reserved.
• Organocatalytic Cloke–Wilson Rearrangement: DABCO-Catalyzed Ring Expansion of Cyclopropyl Ketones to 2,3-Dihydrofurans
  作者：Jingfang Zhang、Yuhai Tang、Wen Wei、Yong Wu、Yang Li、Junjie Zhang、Yuansuo Zheng、Silong Xu

  DOI：10.1021/acs.orglett.7b00805

  日期：2017.6.16

  An organocatalytic Cloke–Wilson rearrangement of cyclopropyl ketones to 2,3-dihydrofurans is exploited utilizing the homoconjugate addition process. With 1,4-diazabicyclo[2.2.2]octane as the catalyst, the rearrangement in DMSO at 120 °C proceeded in generally high yields, exclusive regioselectivity, and a broad substrate scope. An examination of the mechanism including stereochemical analysis and intermediate

  利用均轭共轭加成工艺开发了环丙基酮对2，3-二氢呋喃的有机催化Cloke-Wilson重排。以1,4-二氮杂双环[2.2.2]辛烷为催化剂，在DMSO中于120°C进行的重排通常以高收率，唯一的区域选择性和较宽的底物范围进行。该机构包括立体化学分析和中间隔离支撑一个S的检查Ñ机制的1型环开口。