[chloro-(p-tolylsulfinyl)methylidene]cyclopentane | 644977-00-4

• 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: [chloro-(p-tolylsulfinyl)methylidene]cyclopentane
• 英文别名: 1-[Chloro(cyclopentylidene)methyl]sulfinyl-4-methylbenzene
• CAS: 644977-00-4
• 化学式: C₁₃H₁₅ClOS
• 分子量: 254.781
• InChiKey: PBYXIQPEMHNBCX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  16
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.38
• 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：

  [chloro-(p-tolylsulfinyl)methylidene]cyclopentane 在 N,N-二甲基丙烯基脲 、 异丙基氯化镁 、 sodium hexamethyldisilazane 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 4.33h， 生成 tert-butyl spiro[2.4]heptane-1-carboxylate
  参考文献：
  名称：

  从烯醇锂与 1-氯乙烯基对甲苯基亚砜的共轭加成开始高效合成环丙烷羧酸酯

  摘要：

  使用 1-氯乙烯基对甲苯基亚砜作为关键材料，分三步实现了叔丁基环丙烷羧酸酯的有效合成。锂酯烯醇化物与亚砜的共轭加成以高产率得到4-氯-4-(对-甲苯基亚磺酰基)丁酸叔丁酯。然后在 –60 °C 下通过与 i-PrMgCl 的亚砜-镁交换反应去除所得加合物中的对甲苯基亚磺酰基。脱亚磺酰化产物 4-氯丁酸叔丁酯的环化在 NaHMDS 存在下在 THF-DMPU 混合物中发生，以良好的收率得到环丙烷羧酸叔丁酯。使用具有高对映体过量的旋光 (E)- 和 (Z)-亚砜成功地实现了环丙烷羧酸叔丁基酯的两种对映体的不对称合成。

  DOI：

  10.1055/s-0032-1318168
• 作为产物：
  描述：

  chloromethyl p-tolyl sulfoxide 在 吡啶 、 4-二甲氨基吡啶 、 lithium diphenylamide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 为溶剂， 反应 15.67h， 生成 [chloro-(p-tolylsulfinyl)methylidene]cyclopentane
  参考文献：
  名称：

  螺的新合成，包括不对称合成[4。n ]烯酮，由三部分组成：环酮，氯甲基对甲苯基亚砜和乙腈；和外消旋可乐酮的正式全合成

  摘要：

  由几种环酮和氯甲基对甲苯基亚砜合成了1-氯代戊酰基对甲苯基亚砜，收率很高。在-78°C到室温下，用氰基甲基锂处理1-氯乙烯基对甲苯基亚砜，可以高收率得到螺环烯腈。烯丙腈的酸性处理可得到螺[4]。n ]烯酮，收率高。通过使用不对称的环状酮，α-四氢萘酮和光学活性的氯甲基p-甲苯基亚砜，此方法可提供对映体纯的螺[4.5]癸烯酮，收率高，并且从亚砜手性中心具有出色的不对称诱导性。通过使用该方法，实现了外消旋的螺环倍半萜烯，阿科隆的正式全合成。

  DOI：

  10.1016/j.tet.2003.09.099

文献信息

• A synthesis of bicyclo[n.1.0]alkanes having tert-butyl carboxylate or acetamide moiety via the intramolecular 1,3-CH insertion of magnesium carbenoids
  作者：Shingo Ogata、Hideki Saitoh、Daisuke Wakasugi、Tsuyoshi Satoh

  DOI：10.1016/j.tet.2008.04.024

  日期：2008.6

  enolate of carboxylic acid tert-butyl esters or N,N-dimethylacetamide gave adducts in high yields. The adducts were treated with ether solution of isopropylmagnesium chloride in dry toluene to give bicyclo[n.1.0]alkane derivatives having tert-butyl carboxylate or acetamide moiety on the bridgehead carbon in high to quantitative yields via magnesium carbenoid 1,3-CH insertion reaction. The 1,3-CH insertion

  1-氯乙烯基治疗p -甲苯基砜，来自各种环酮和氯甲基衍生的p -甲苯基砜，与锂羧酸的烯醇叔丁基酯或Ñ，ñ二甲基乙酰胺，得到高收率的加合物。该加合物在干燥的甲苯与异丙基氯化镁的乙醚溶液处理，得到双环[ Ñ .1.0]具有烷衍生物叔通过羧甲基1,3-CH插入反应，桥头碳上的羧酸丁酯或乙酰胺部分以高产率或定量产率产生。1,3-CH插入反应被证明具有区域选择性和立体特异性。讨论了反应机理以及选择性和特异性的起源。
• Coupling Reaction of Magnesium Alkylidene Carbenoids with α-Sulfonyl­allyllithiums: An Efficient Route to Multi-Substituted Vinylallenes
  作者：Tsuyoshi Satoh、Tsutomu Kimura、Gen Kobayashi、Masashi Ishigaki、Mio Inumaru、Jo Sakurada

  DOI：10.1055/s-0032-1317507

  日期：——

  sulfoxides and allyl or vinyl sulfones. Allyl and vinyl sulfones served as α-sulfonylallyllithium sources were prepared from carbonyl compounds in three or four steps in good overall yields. The coupling reaction of α-sulfonylallyllithiums with magnesium alkylidene carbenoids, which were generated from 1-chlorovinyl p-tolyl sulfoxides and isopropylmagnesium chloride, afforded multi-substituted vinylallenes

  摘要 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。 从1-氯乙烯基对甲苯基亚砜和烯丙基或乙烯基砜成功地合成了各种乙烯基烯丙基。由羰基化合物分三步或四步以良好的总收率制备用作α-磺酰基烯丙基锂的烯丙基和乙烯基砜。α-磺酰基烯丙基锂与由1-氯乙烯基对甲苯基亚砜和异丙基氯化镁生成的亚烷基镁类胡萝卜素的偶合反应以高达88％的产率提供了多取代的乙烯基烯。
• A versatile synthesis, including asymmetric synthesis, of bicyclo[n.1.0]alkanes from cyclic ketones via the magnesium carbenoid 1,3-CH insertion as a key reaction
  作者：Tsuyoshi Satoh、Shingo Ogata、Daisuke Wakasugi

  DOI：10.1016/j.tetlet.2006.07.140

  日期：2006.10

  1-chlorovinyl p-tolyl sulfoxides, which were synthesized from various cyclic ketones and chloromethyl p-tolyl sulfoxide in three steps, in high yields, with lithium enolate of tert-butyl acetate or its homologues gave the adducts in quantitative yields. The adducts were treated with isopropylmagnesium chloride in ether in dry toluene as the reaction solvent to afford bicyclo[n.1.0]alkanes in high to quantitative

  用乙酸叔丁酯的烯醇锂或其同系物分三步高产率地处理由各种环酮和氯甲基对甲苯基亚砜合成的1-氯乙烯基对甲苯基亚砜，以定量收率得到加合物。该加合物用在乙醚中的异丙基氯化镁的无水甲苯处理作为反应溶剂，得到双环[ Ñ .1.0]在经由镁高至定量的产率的烷烃类卡宾1,3- CH插入。当此方法进行从非对称的环酮起始和（- [R ）氯甲基p -甲苯基砜，二环的不对称合成[ Ñ .1.0]烷烃被实现。
• Alkenylation of 1- and 2-Naphthols by Using Magnesium Alkylidene Carbenoids as Electrophilic Alkenylating Agents
  作者：Tsuyoshi Satoh、Tsutomu Kimura、Masaya Watanabe、Gaku Kashiwamura、Jo Sakurada

  DOI：10.1055/s-0032-1318132

  日期：——

  1- and 2-Naphthols were successfully alkenylated in a regioselective manner by treating the corresponding lithium 1- and 2-naphtholates with magnesium alkylidene carbenoids. The magnesium alkylidene carbenoids were generated in situ by a sulfoxide-magnesium exchange reaction of 1-chlorovinyl 4-tolyl sulfoxides with isopropylmagnesium chloride. The reaction of magnesium alkylidene carbenoids with lithium 2-naphtholates took place at the 1-position of the naphthyl ring to give 1-(alk-1-enyl)-2-naphthols in respectable yields. The alkenylation of 1-naphthols proceeded at the 2-position of the naphthol ring to give 2-(alk-1-enyl)-1-naphthols in yields of 56-67%. In contrast to the reaction of lithium naphtholates with magnesium alkylidene carbenoids, the reaction of lithium phenolates gave low yields of the corresponding alk-1-enyl aryl ethers.
• Efficient one-pot synthesis of 1-chlorovinyl <i>p</i> -tolyl sulfoxides from aldehydes and ketones by the Horner-Wadsworth-Emmons reaction
  作者：Tsutomu Kimura、Gen Kobayashi、Shiori Ijima、Sae Saito、Aki Imafuji、Tsuyoshi Satoh

  DOI：10.1002/hc.21395

  日期：2017.9

  AbstractA variety of 2‐monosubstituted and 2,2‐disubstituted 1‐chlorovinyl p‐tolyl sulfoxides was synthesized through a one‐pot procedure by the Horner‐Wadsworth‐Emmons reaction of carbonyl compounds with [chloro(diethoxyphosphoryl)(p‐tolylsulfinyl)methyl]lithium, which was generated from diethyl chlorophosphate, chloromethyl p‐tolyl sulfoxide, and lithium diisopropylamide in advance. The in situ‐prepared sulfoxides were directly converted into alkynes via the sulfoxide/magnesium exchange reaction with i‐PrMgCl and the subsequent Fritsch‐Buttenberg‐Wiechell rearrangement of the resulting magnesium alkylidene carbenoids.