(+)-(2R)-2-allyl-2-(p-toluenesulfenyl)cyclohexanone | 128402-77-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (+)-(2R)-2-allyl-2-(p-toluenesulfenyl)cyclohexanone
• 英文别名: (R)-(+)-2-Allyl-2-(p-toluenesulfenyl)cyclohexanone；(2R)-2-(4-methylphenyl)sulfanyl-2-prop-2-enylcyclohexan-1-one
• CAS: 128402-77-7
• 化学式: C₁₆H₂₀OS
• 分子量: 260.4
• InChiKey: OJMBDKVXJGWSMD-INIZCTEOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (S)-3-Methyl-2-[2-p-tolylsulfanyl-cyclohex-(Z)-ylideneamino]-butyric acid allyl ester 在 四(三苯基膦)钯 盐酸 、 三苯基膦 作用下， 以 四氢呋喃 为溶剂， 生成 (-)-(2S)-2-allyl-2-(p-toluenesulfenyl)cyclohexanone 、 (+)-(2R)-2-allyl-2-(p-toluenesulfenyl)cyclohexanone
  参考文献：
  名称：

  Hiroi, Kunio; Koyama, Toshihiro; Anzai, Kaori, Chemistry Letters, 1990, # 2, p. 235 - 238

  摘要：

  DOI：

文献信息

• Free-radical cyclization of enantiomerically enriched 2-p-tolylthio derivatives of 2-allylcyclohexanones with Mn(III): asymmetric synthesis of bridged bicyclic ketones and thiochroman-3-ones
  作者：J.L Garcı́a-Ruano、A Rumbero

  DOI：10.1016/s0957-4166(99)00467-x

  日期：1999.11

  enriched 2-allyl-2-(p-tolylsulfonyl)-cyclohexanone 4 and 2-allyl-2-(p-tolylsulfenyl)cyclohexanone 9 are reported. The observed chemoselectivity (reaction on the allylic double bond yielding bridged bicyclic ketones vs. reaction on the aromatic ring of the p-tolyl group affording thiochroman-3-ones) depends on the sulfur function (sulfone or thioether, respectively), which determines the electronic density

  报道了对映体富集的2-烯丙基-2-（对甲苯磺酰基）-环己酮4和2-烯丙基-2-（对甲苯磺酰基）环己酮9的基于Mn（III）的氧化分子内环化。观察到的化学选择性（在烯丙基双键上生成桥联双环酮的反应与在对甲苯基上生成硫代色烷-3-酮的芳香环上的反应）分别取决​​于硫官能团（分别为砜或硫醚），这决定了对甲苯基环的电子密度和起始化合物的构象偏好。C-2上取代基的性质与内/外相关 环化的选择性以及烯酮形成中的区域选择性。
• Asymmetric induction reactions. V. The palladium-catalyzed asymmetric .alpha.-allylation of carbonyl compounds with chiral allyl esters via enamines and imines
  作者：Kunio Hiroi、Jun Abe、Kyoko Suya、Shuko Sato、Toshihiro Koyama

  DOI：10.1021/jo00080a033

  日期：1994.1

  A novel and excellent method for asymmetric alpha-allylation of carbonyl compounds via their chiral enamines or imines bearing allyl eaters has been developed. Readily available chiral allyl eaters having chirality at the alpha-position of the eater carbonyl group, such as (S)-proline and other (S)-alpha-amino acid allyl esters, have been found to serve as good asymmetric allylating reagents in palladium-catalyzed reactions of the chiral enamines and imines derived from them. The use of (S)-proline or (S)-valine allyl esters as the amino parts in the enamines or imines provided the highest optical yields of the corresponding alpha-allyl carbonyl compounds. A mechanism for asymmetric induction is proposed based on the stereochemical results obtained.