丁醛,3-甲基-2-(苯基硫代)- | 132331-33-0

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 中文名称: 丁醛,3-甲基-2-(苯基硫代)-
• 英文名称: (S/R)-2-(phenylsulfanyl)-3-methylbutanal
• 英文别名: (2RS)-3-Methyl-2-phenylsulfanylbutanal；3-methyl-2-(phenylthio)butanal；3-methyl-2-phenylsulfanyl-butyraldehyde；3-Methyl-2-phenylsulfanylbutanal
• CAS: 132331-33-0
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: DDIMAOMJLRHPJF-UHFFFAOYSA-N

物化性质

• 沸点：
  269.7±23.0 °C(Predicted)
• 密度：
  1.05±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  丁醛,3-甲基-2-(苯基硫代)- 在 锂硼氢 、 三氟甲磺酸二丁硼 、 水 、 氯化二乙基铝 、 N,N-二异丙基乙胺 作用下， 反应 1.67h， 生成 (2R,3S,4R)-3-Hydroxy-2,5-dimethyl-4-phenylsulfanylhexan-1-ol
  参考文献：
  名称：

  与外消旋2-苯硫基醛的反醛醇缩合反应的动力学拆分：苯硫醚迁移的环状醚和内酯的不对称合成

  摘要：

  在路易斯酸催化的酰亚胺化硼烯酸酯（2）与外消旋2-苯硫基醛（3a）–（3c）的不对称反羟醛反应中的动力学拆分可得到良好的反，反羟醛（7）收率。描述了手性环状醚（4a）-（4c）和（5a）-（5c）的合成，以及制备手性内酯（6a）-（6c）的简单新途径。

  DOI：

  10.1016/s0040-4039(00)74262-6
• 作为产物：
  描述：

  异戊酸乙酯 在 lithium aluminium tetrahydride 、 二甲基亚砜 、 二异丙胺 、 三氟乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.17h， 生成 丁醛,3-甲基-2-(苯基硫代)-
  参考文献：
  名称：

  Do the Electronic Effects of Sulfur Indeed Control the π-Selectivity of γ-Sulfenyl Enones? An Investigation

  摘要：

  The electronic effects of sulfur in gamma-sulfenyl enones are not transmitted to the carbonyl carbon through the pi bond as reported previously. The diastereoselectivity is rather controlled by a combination of several other factors. The steric effects arising from the substituents on the sulfur atom and the gamma-carbon and the bulk of the nucleophile constitute the major control elements.

  DOI：

  10.1021/jo034608c

文献信息

• [EN] ORGANOCATALYSTS AND METHODS OF USE IN CHEMICAL SYNTHESIS<br/>[FR] ORGANOCATALYSEURS ET PROCEDES D'UTILISATION DE CES DERNIERS DANS LA SYNTHESE CHIMIQUE
  申请人：STC UNM

  公开号：WO2006007586A1

  公开（公告）日：2006-01-19

  The present invention pertains generally to compositions comprising organocatalysts that facilitate stereo-selective reactions and the method of their synthesis and use. Particularly, the invention relates to metal-free organocatalysts for facilitation of stereo-­selective reactions, and the method of their synthesis and use. These compounds have the structure of the Formulas (I) and (II). Where X is independently selected from CH2, N-Ra, O, S or C=O; Y is CH2, N-Ra, O, S or C=O, with the proviso that at least one of X or Y is CH2, and preferably both of X and Y are CH2; Ra is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 alkyl including a C3-C6 cyclic alkyl group, or an optionally substituted aryl group, preferably an optionally substituted phenyl group; Rb is H, an optionally substituted C1-C12 alkyl, preferably an optionally substituted C1-C6 acyclic or a a C3-C6 cyclic alkyl group, CHO, N(Me)O, CO(S)Ra or the group of Formula (III). Where Rc and Rd are each independently H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C12 alkyl, more preferably a C1-C6 alkyl, and an optionally substituted aryl group, or together Rc and Rd form an optionally substituted carbocyclic or optionally substituted heterocyclic ring; R1 is OH, OR, NR'R', NHC(=O)R, NHSO2R; R2 is H, F, C1, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1­C6 alkyl, an optionally substituted aryl group or a =O group (which establishes a carbonyl group with the carbon to which =O is attached; R3 is H, OH, F, C1, Br, I, Cl, an optionally substituted C1-C20 alkyl, alkenyl or alkynyl ('hydrocarbyl') group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl, such that the carbon to which R3 is attached has an R or S configuration; R is H, an optionally substituted C1-C20 alkyl, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group, R' and R' are each independently H, an optionally substituted C1-C20 alkyl group, preferably an optionally substituted C1-C6 alkyl, or an optionally substituted aryl group; or together R' and R' form an optionally substituted heterocyclic, preferably a 4 to 7 membered optionally substituted heterocyclic group or an optionally substituted heteroaryl ring with the nitrogen to which R' and R' are attached; and wherein said compound is free from a metal catalyst.

  本发明涉及一般包括有机催化剂的组合物，该催化剂促进立体选择性反应以及其合成和使用方法。特别地，本发明涉及无金属有机催化剂以促进立体选择性反应，以及其合成和使用方法。这些化合物具有以下结构的式（I）和（II）。其中X独立地选择自CH2、N-Ra、O、S或C=O；Y为 、N-Ra、O、S或C=O，但至少X或Y中的一个为 ，最好是X和Y都为 ；Ra为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6烷基，包括C3-C6环烷基，或可选择地取代的芳基，最好是可选择地取代的苯基；Rb为H、可选择地取代的C1-C12烷基，最好是可选择地取代的C1-C6无环或C3-C6环烷基，CHO、N(Me)O、CO(S)Ra或式（III）的基团。其中Rc和Rd各自独立地为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C12烷基，更好地是C1-C6烷基，以及可选择地取代的芳基，或者Rc和Rd一起形成可选择地取代的碳环或可选择地取代的杂环；R1为OH、OR、NR'R'、NHC(=O)R、NHSO2R；R2为H、F、C1、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，可选择地取代的芳基或=O基团（与=O连接的碳形成羰基基团）；R3为H、OH、F、C1、Br、I、Cl、可选择地取代的C1-C20烷基、烯基或炔基（'烃基'），最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，使得R3连接的碳具有R或S构型；R为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基，R'和R'各自独立地为H、可选择地取代的C1-C20烷基，最好是可选择地取代的C1-C6烷基，或可选择地取代的芳基；或者R'和R'一起形成可选择地取代的杂环，最好是4到7成员的可选择地取代的杂环基团或与R'和R'连接的氮原子形成可选择地取代的杂芳基环；其中所述化合物不含金属催化剂。
• Synthesis of Enantiomerically Enriched α-Sulfenylated Ketones and Aldehydes
  作者：Joo-Hack Youn、Rudolf Herrmann、Ivar Ugi

  DOI：10.1055/s-1987-27870

  日期：——

  α-Sulfenylated carbonyl compounds are prepared by the reaction of imines of aldehydes and ketones containing α-hydrogens with disulfides via the metalloenamines. With (R)-α-phenylethylamine as chiral auxiliary, enantiomeric excesses of 13-51% are observed.

  通过含有α-氢的醛和酮的亚胺与二硫化物的反应，利用金属烯胺制备α-硫代羰基化合物。以(R)-α-苯乙胺作为手性辅助剂，观察到13-51%的对映体过量。
• Kinetic resolution in asymmetric anti aldol reactions of branched and straight chain racemic 2-phenylsulfanyl aldehydes: asymmetric synthesis of cyclic ethers and lactones by phenylsulfanyl migration
  作者：Kelly Chibale、Stuart Warren

  DOI：10.1039/p19960001935

  日期：——

  The kinetic resolution of branched and straight chain 2-phenylsulfanyl aldehydes by the Lewis acid-catalysed asymmetric anti aldol reaction followed by reduction to single enantiomers of 1,3-diols and/or acid-catalysed cyclisation with PhS migration provides a route to enantiomerically pure cyclic ethers and lactones with full stereochemical control.

  分支和直链2-苯基硫醇醛的动力学分辨通过路易斯酸催化的非对称反反应后还原为1,3-二醇的单一对映体和/或酸催化的环化反应并伴随PhS迁移，为获得具有完全立体化学控制的对映体纯的环氧乙烷和乳酸酯提供了一条途径。
• Exopericyclic stereocontrol in Johnson–Claisen rearrangements of allylic sulfides
  作者：Donald Craig、John W. Harvey、Alexander G. O'Brien、Andrew J. P. White

  DOI：10.1039/c0cc01039a

  日期：——

  A study of the effects of exopericyclic stereocentres on the stereoselectivity of Johnson–Claisen rearrangements of thioether-containing allylic alcohols shows that selectivity is highly dependent upon allylic substitution patterns.

  一项关于外环立体中心对含硫醚烯丙基醇的约翰逊-克莱森重排立体选择性影响的研究表明，选择性在很大程度上取决于烯丙基取代模式。
• The synthesis of optically active 2-phenylthio aldehydes
  作者：Kelly Chibale、Stuart Warren

  DOI：10.1016/s0040-4039(00)76722-0

  日期：1994.6

  Optically active linear and branched chain 2-phenylthio aldehydes can be made in high optical purity (up to > 98% e.e.) by sulfenylation of a phenylalanine-derived oxazolidinone imide, reduction and re-oxidation with the Dess-Martin reagent even though the products enolise easily.

  通过苯丙氨酸衍生的恶唑烷二酮亚胺的亚磺酰化，用Dess-Martin试剂还原和再氧化，可以制备光学活性的直链和支链2-苯硫基醛，具有较高的光学纯度（最高> 98％ee）。容易犯规。