(Z)-1-chloro-2-methyl-4-phenyl-1-(p-tolylsulfinyl)-1-butene

• 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: (Z)-1-chloro-2-methyl-4-phenyl-1-(p-tolylsulfinyl)-1-butene
• 英文别名: 1-[(Z)-1-chloro-2-methyl-4-phenylbut-1-enyl]sulfinyl-4-methylbenzene
• 化学式: C₁₈H₁₉ClOS
• 分子量: 318.867
• InChiKey: WXSGGDFNXJNWOJ-OBGWFSINSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  21
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.22
• 拓扑面积：
  36.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (Z)-1-chloro-2-methyl-4-phenyl-1-(p-tolylsulfinyl)-1-butene 在 二异丁基氢化铝 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  区域特异性镁类胡萝卜素1,3-CH插入的第一个例子：其机理和立体化学

  摘要：

  由不对称酮和氯甲基对甲苯基亚砜衍生的1-氯乙烯基对甲苯基亚砜的两个几何异构体与乙酸叔丁酯的烯醇锂的加成反应分别得到加合物的单一异构体。用i -PrMgCl处理每种非对映异构体导致形成镁类胡萝卜素。发现由类胡萝卜素镁发生高度区域特异性的1，3-CH插入反应，从而以高收率提供环丙烷。讨论了加合物的立体化学，反应机理和区域特异性的起源。

  DOI：

  10.1016/j.tetlet.2007.05.101

文献信息

• A method for the synthesis of cyclopropanes by regiospecific and regioselective magnesium carbenoid 1,3-CH insertion as the key reactions
  作者：Hiroyuki Watanabe、Shingo Ogata、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2010.05.061

  日期：2010.7

  i-PrMgCl resulted in the formation of magnesium carbenoid. Highly regiospecific 1,3-CH insertion reaction was found to take place from each magnesium carbenoid to afford cyclopropanes. On the other hand, when the unsymmetrical ketones bearing an oxygen- or a nitrogen-functional group on the α-carbon were used in this procedure, the regioselective 1,3-CH insertion reaction proceeded mainly. Stereochemistry

  衍生自不对称酮和氯甲基对甲苯基亚砜的1-氯乙烯基对甲苯基亚砜的两个几何异构体与乙酸叔丁酯的烯醇锂的加成反应分别得到加合物的单一非对映异构体。用i处理每个非对映异构体-PrMgCl导致形成类镁镁。发现每个镁类胡萝卜素都发生高度区域特异性的1,3-CH插入反应，从而生成环丙烷。另一方面，当在该方法中使用在α-碳上带有氧或氮官能团的不对称酮时，区域选择性的1，3-CH插入反应主要进行。讨论了加合物的立体化学，反应机理以及特异性和选择性的实质。
• A novel direct N-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids
  作者：Tsuyoshi Satoh、Jo Sakurada、Yumi Ogino

  DOI：10.1016/j.tetlet.2005.05.058

  日期：2005.7

  Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at −78 °C in toluene, with N-lithio nitrogen-containing heterocycles (e.g., indole, indazole, phenothiazine, and phenoxazine) gave N-alkenylated products in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion, which could

  在异丙基氯化镁中，于-78°C在甲苯中，用N-硫代含氮杂环（例如，吲哚，吲唑，吩噻嗪和吩恶嗪）处理1-氯乙烯基对甲苯基亚砜生成的亚烷基镁类胡萝卜素，得到N链烯基化产物，产率中等至良好。发现该反应的中间体是烯基阴离子，其可以使用CuI作为催化剂用碘代烷烃捕获，以在氮上得到具有完全取代的烯烃的杂环。烯基阴离子中间体也可以被苯甲酰氯和异氰酸苯酯捕集。该反应提供了含氮杂环的相当新颖和直接的N-烯基化。
• Reaction of magnesium alkylidene carbenoids with lithium acetylides and lithium thiolates: a novel synthesis of conjugated enynes and vinyl sulfides
  作者：Masanori Watanabe、Masatomo Nakamura、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2005.02.084

  日期：2005.5

  carbenoids were generated from 1-chlorovinyl p-tolyl sulfoxides with i-PrMgCl at −78 °C in THF or toluene via the sulfoxide–magnesium exchange reaction. Reaction of the generated magnesium alkylidene carbenoids with lithium acetylides or lithium thiolates gave conjugated enynes or vinyl sulfides, respectively, in moderate to good yields. The intermediate of this reaction was found to be the alkenyl anion and

  亚烷基镁的类胡萝卜素是在1-78℃于THF或甲苯中，由1-氯乙烯基对甲苯基亚砜与i -PrMgCl经由亚砜-镁交换反应生成的。产生的亚烷基镁类胡萝卜素与乙炔化锂或硫醇锂反应，分别以中等至良好的产率得到共轭烯炔或乙烯基硫化物。发现该反应的中间体是链烯基阴离子，它可以被一些亲电试剂捕获，得到四取代的共轭烯炔和乙烯基硫化物。
• A novel route to fully substituted cyanoallenes from three components, ketones, chloromethyl p-tolyl sulfoxide, and nitriles, via α-bromocyclopropyl p-tolyl sulfoxides
  作者：Tsuyoshi Satoh、Youhei Gouda

  DOI：10.1016/j.tetlet.2006.01.161

  日期：2006.4

  Treatment of 1-chlorovinyl p-tolyl sulfoxides. which were derived front ketones and chloromethyl p-tolyl sulfoxide in high yields, with lithium alpha-carbanion of nitriles gave the adducts in quantitative yields. The adducts were converted to alpha-bromocyclopropyl p-tolyl sulfoxides in two steps in good yields. Finally, the sulfoxides were treated with excess lithium carbanion of isobutyronitrile to afford fully Substituted cyanoallenes in high to quantitative yields via sulfoxide-lithium exchange reaction. This procedure offers a novel synthetic method for fully substituted cyanoallenes with coupling of three components (ketones, chloromethyl p-tolyl sulfoxide, and nitriles) in good overall yields. (c) 2006 Elsevier Ltd. All rights reserved.
• Direct N- and C-alkenylation of nitrogen-containing heterocycles with magnesium alkylidene carbenoids
  作者：Jo Sakurada、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2007.02.072

  日期：2007.4

  Treatment of magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides with isopropylmagnesium chloride at -78 degrees C in toluene, with N-lithio nitrogen-containing heterocycles gave N-alkenylated products in moderate to good yields. Also, the reaction of C-lithio indoles, which were generated from N-protected indoles, with magnesium alkylidene carbenoids gave C-2 or C-3 alkenylated products, corresponding to the protective group. The intermediate of these reactions were found to be the alkenyl anion, which could be trapped with electrophiles to give the heterocycles having fully substituted alkenes. (C) 2007 Elsevier Ltd. All rights reserved.