(S_S)-menthyl p-toluenesulfinate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (S_S)-menthyl p-toluenesulfinate
• 英文别名: menthyl [S(S)]-p-toluenesulfinate；(S)-1-menthyl p-toluenesulfinate；menthyl (S)-p-toluenesulfinate；menthyl p-toluenesulfinate；(5-methyl-2-propan-2-ylcyclohexyl) (R)-4-methylbenzenesulfinate
• 化学式: C₁₇H₂₆O₂S
• 分子量: 294.458
• InChiKey: NQICGNSARVCSGJ-JTTVCCKGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.3
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (S_S)-menthyl p-toluenesulfinate 在 N-溴代丁二酰亚胺(NBS) 、 正丁基锂 作用下， 以 四氢呋喃 、 乙腈 为溶剂， 反应 18.0h， 生成 [S(S)]-5-bromo-1,4-dimethoxy-2-(p-tolylsulfinyl)benzene
  参考文献：
  名称：

  Photoinduced Conformational Switch of Enantiopure Azobenzenes Controlled by a Sulfoxide

  摘要：

  Two series of enantiopure azobenzenes with a p-tolylsulfoxide at the ortho or meta position with respect to the azo group, have been regioselectively synthesized. Both can act as enantiopure molecular switches showing different structural features owing to the presence of the stereogenic sulfur. The photoisomerization process, studied by UV-vis, circular dichroism (CD), NMR, and chiral HPLC evidenced a double role of the sulfoxide. A transfer of chirality from the sulfoxide to the azo system was observed by CD in both cis and trans-isomers of the meta sulfinyl derivatives 3, whereas this perturbation was evident for the ortho sulfinyl series 7 only in the cis isomer. The NMR study evidenced that the s-cis rigid conformation of the bisaromatic sulfoxide was fixing a different orientation of the overall system in each series both in the trans and cis isomers, by forcing a final U-shaped structure in cis-3 and an S-shaped structure in cis-7. Very different values of specific optical rotations were measured in both trans and cis isomers, also reflecting the existence of distinct chiral entities in the photostationary states. The easy and reversible changes occurring between different conformational states could find applications in the photocontrol of several molecular switches.

  DOI：

  10.1021/ja070163o
• 作为产物：
  描述：

  对甲苯亚磺酸 在 氯化亚砜 、 silica gel 作用下， 反应 0.77h， 生成 (S_S)-menthyl p-toluenesulfinate
  参考文献：
  名称：

  ONE-POT AND SIMPLE REACTION FOR THE SYNTHESIS OF ALKYL p-TOLUENESULFINATE ESTERS UNDER SOLID-PHASE CONDITIONS

  摘要：

  A manipulatively one-pot and rapid method for the synthesis of alkyl p-toluenesulfinate esters 1 from p-toluenesulfinic acid, supported thionyl chloride on silica gel and aliphatic alcohols in solid phase conditions is described.

  DOI：

  10.1080/10426500008043672

文献信息

• Asymmetric Synthesis of the Tetrahydropyran Ring, C32−C38 Fragment, of Phorboxazoles
  作者：Yasmin Brinkmann、M. Carmen Carreño、Antonio Urbano、Françoise Colobert、Guy Solladié

  DOI：10.1021/ol048099s

  日期：2004.11.1

  of phorboxazoles, (2R,4R,6R)-1, is described using a sulfoxide as chiral auxiliary. Key advances include the stereoselective reductions of beta-keto- or beta,gamma-diketosulfoxides, the acid-catalyzed cyclization of enantiopure sulfinyl hydroxy ketone precursors to the tetrahydropyran ring, and the Pummerer reaction on the pendant sulfoxide to create the formyl group.

  使用亚砜作为手性助剂描述了模型醛（2R，6R）-2和佛波唑的C32-C38片段（2R，4R，6R）-1的不对称合成。关键的进展包括立体选择性地还原β-酮或β，γ-二酮亚砜，对映体纯的亚磺酰基羟基酮前体到四氢吡喃环的酸催化环化以及亚砜侧基上的Pummerer反应产生甲酰基。
• Axial Chirality Control During Suzuki−Miyaura Cross-Coupling Reactions: The <i>tert</i>-Butylsulfinyl Group as an Efficient Chiral Auxiliary
  作者：Françoise Colobert、Victoria Valdivia、Sabine Choppin、Frédéric R. Leroux、Inmaculada Fernández、Eleuterio Álvarez、Noureddine Khiar

  DOI：10.1021/ol9020755

  日期：2009.11.19

  An efficient route to a new family of axially chiral biaryl ligands by a Suzuki−Miyaura cross-coupling reaction between ortho,ortho′-disubstituted aryl iodides bearing in ortho position a tert-butyl or p-tolylsulfinyl group and ortho-substituted phenyl boronic acids or esters is described. The comparison between the t-BuSO and p-TolSO groups as chiral controllers is reported. The modularity of the

  通过位于邻位的叔丁基或对甲苯硫亚磺酰基的邻，邻′-二取代的芳基碘化物与邻位取代的苯基硼酸之间的Suzuki-Miyaura交叉偶联反应，可以有效地开发新的轴向手性联芳基配体家族描述了酯。报道了在t -BuSO和p -TolSO基团作为手性控制剂之间的比较。通过制备各种对映体纯的轴向手性混合S / N和S / P配体证明了该方法的模块化。
• Asymmetric Synthesis of Aryl Benzyl Sulfoxides by Vanadium-Catalysed Oxidation: A Combination of Enantioselective Sulfide Oxidation and Kinetic Resolution in Sulfoxide Oxidation
  作者：Pádraig Kelly、Simon E. Lawrence、Anita R. Maguire

  DOI：10.1002/ejoc.200600320

  日期：2006.10

  Enantioselective vanadium-catalysed oxidation of aryl benzyl sulfides using Bolm’s procedure is accompanied by kinetic resolution in the oxidation of the resulting sulfoxides which enhances the enantiopurities of the sulfoxides recovered (typically >90 % ee), albeit with an associated reduction in yield. The effects of ligand, solvent and reaction conditions are discussed in detail.(© Wiley-VCH Verlag

  使用 Bolm 程序对芳基苄基硫化物进行对映选择性钒催化氧化伴随着所得亚砜氧化的动力学拆分，这提高了回收的亚砜的对映纯度（通常 >90% ee），尽管伴随着产率的降低。详细讨论了配体、溶剂和反应条件的影响。 (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)
• Chiral sulfur derivatives in the allylation of acyl hydrazones: C2-symmetric bis-sulfinamides as enhanced chiral organic promoters.
  作者：Inmaculada Fernández、Ana Alcudia、Beatrice Gori、Victoria Valdivia、Rocío Recio、María Victoria García、Noureddine Khiar

  DOI：10.1039/c0ob00078g

  日期：——

  Monosulfinamides and C2-symmetric bis-sulfinamides are convenient neutral chiral promoters in the allylation of acyl hydrazones, the nature of the spacer and the substituent at the sulfinyl sulfur are key elements for the enantioselectivity of the process.

  在酰基肼的烯丙基化过程中，单亚磺酰胺和 C2 对称双亚磺酰胺是一种方便的中性手性促进剂，间隔物的性质和亚磺酰基硫上的取代基是该过程对映选择性的关键因素。
• Asymmetric synthesis of β-hydroxythioacetamides mediated by enantiomerically pure sulphiny1 derivatives
  作者：Mauro Cinquini、Amedea Manfredi、Henriette Molinari、Angelo Restelli

  DOI：10.1016/s0040-4020(01)96733-x

  日期：1985.1

  Enantiomerically pure P-tolyl sulphinyl-N,N-dimethylthioacetamide (1) was prepared starting from (-)-(S)-menthyl toluene-p-sulphinate. Aldol-type condensation of (1) and subsequent removal of the Sulphinyl group open an entry to optically active β-hydroxy thioacetamides in 40–90% e.e.

  从（-）-（S）-薄荷基甲苯-对-硫酸酯开始制备对映体纯的对甲苯基亚磺酰基-N，N-二甲基硫代乙酰胺（1）。（1）的醛醇缩合反应和随后的亚磺酰基基团的去除打开了在40-90％ee中进入旋光性β-羟基硫代乙酰胺的通道