(4E)-1-[(4S)-4-benzyl-2-thioxo(1,3-thiazolidin-3-yl)](2S,3S)-3-hydroxy-methyl-5-phenylpent-4-en-1-one | 425603-04-9

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 肉桂醇
• 英文名称: (4E)-1-[(4S)-4-benzyl-2-thioxo(1,3-thiazolidin-3-yl)](2S,3S)-3-hydroxy-methyl-5-phenylpent-4-en-1-one
• 英文别名: (E,2S,3S)-1-[(4S)-4-benzyl-2-sulfanylidene-1,3-thiazolidin-3-yl]-3-hydroxy-2-methyl-5-phenylpent-4-en-1-one
• CAS: 425603-04-9
• 化学式: C₂₂H₂₃NO₂S₂
• 分子量: 397.562
• InChiKey: DWUOHBDDFNKIFI-ARSMWMFXSA-N

物化性质

• 沸点：
  582.9±60.0 °C(predicted)
• 密度：
  1.28±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  27
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  97.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4E)-1-[(4S)-4-benzyl-2-thioxo(1,3-thiazolidin-3-yl)](2S,3S)-3-hydroxy-methyl-5-phenylpent-4-en-1-one 在 咪唑 、 二异丁基氢化铝 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 反应 8.0h， 生成
  参考文献：
  名称：

  13-脱甲基lyngbyaloside B的全合成

  摘要：

  已经实现了13-去甲基lyngbyaloside B的全合成，这是海洋大环内酯糖苷lyngbyaloside B的非天然类似物。通过酯化和闭环复分解以聚合方式构建14元大环骨架。通过Stille型反应和随后的溴代甲硅烷基化引入溴代二烯侧链。最后，在Schmidt条件下通过糖基化立体选择性地引入鼠李糖吡喃糖单元。

  DOI：

  10.1021/ol400408w
• 作为产物：
  描述：

  (E)-(2S,3S)-1-((S)-4-Benzyl-2-thioxo-thiazolidin-3-yl)-2-methyl-5-phenyl-3-trimethylsilanyloxy-pent-4-en-1-one 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 1.5h， 生成 (4E)-1-[(4S)-4-benzyl-2-thioxo(1,3-thiazolidin-3-yl)](2S,3S)-3-hydroxy-methyl-5-phenylpent-4-en-1-one
  参考文献：
  名称：

  Alkene Metathesis Approach to β-Unsubstituted Anti-Allylic Alcohols and Their Use in Ene–Yne Metathesis

  摘要：

  The synthesis of beta-unsubstituted, anti-allylic alcohols using a catalytic Evans aldol reaction conjoined with a relay-type ring-closing alkene metathesis is reported. The metathesis step serves to remove a beta-alkenyl group, which facilitated the aldol step. The beta-substituted enals serve as acrolein surrogates. The products were employed in ene-yne cross metathesis.

  DOI：

  10.1021/jo202398q

文献信息

• Stereoselective Total Synthesis of Bistramide A
  作者：J. S. Yadav、Lakshindra Chetia

  DOI：10.1021/ol702095n

  日期：2007.10.1

  A highly stereoselective and convergent total synthesis of bistramide A is described. The salient feature of this synthesis is the construction of the spiroketal subunit by hydrolysis of dialkylated tosylmethyl isocyanide derivative derived via alkylation of TosMIC with suitably substituted halohydrin derivatives.

  描述了双立体酰胺A的高度立体选择性和收敛的全合成。该合成的显着特征是通过将TosMIC与合适取代的卤代醇衍生物进行烷基化而衍生的二烷基化的甲苯磺酰基甲基异氰化物衍生物的水解来构建螺环亚基。
• Magnesium Halide-Catalyzed Anti-Aldol Reactions of Chiral <i>N</i>-Acylthiazolidinethiones
  作者：David A. Evans、C. Wade Downey、Jared T. Shaw、Jason S. Tedrow

  DOI：10.1021/ol025553o

  日期：2002.4.1

  [reaction: see text] Diastereoselective direct aldol reactions of chiral N-acylthiazolidinethiones occur in high yield with preference for the illustrated anti diastereomer. This reaction is catalyzed by 10% MgBr2.OEt2 in the presence of triethylamine and chlorotrimethylsilane. Yields range from 56 to 93% with diastereoselectivity up to 19:1 for a variety of N-acylthiazolidinethiones and unsaturated

  [反应：见正文]手性N-酰基噻唑烷硫酮的非对映选择性直接羟醛反应以高收率发生，优选图示的抗非对映异构体。在三乙胺和氯代三甲基硅烷的存在下，该反应由10％MgBr2.OEt2催化。对于各种N-酰基噻唑烷硫酮和不饱和醛，非对映选择性高达19：1，产率为56％至93％。
• Rhodium-catalyzed asymmetric hydroboration of γ,δ-unsaturated amide derivatives: δ-borylated amides
  作者：G. L. Hoang、S. Zhang、J. M. Takacs

  DOI：10.1039/c8cc01563e

  日期：——

  γ,δ-Unsaturated amides in which the alkene moiety bears an aryl or heteroaryl substituent undergo regioselective rhodium-catalyzed δ-borylation by pinacolborane to afford chiral secondary benzylic boronic esters. The results contrast the γ-borylation of γ,δ-unsaturated amides in which the disubstituted alkene moiety bears only alkyl substituents; the reversal in regiochemistry is coupled with a reversal

  γ，δ-不饱和酰胺（其中烯基部分带有芳基或杂芳基取代基）通过频哪醇硼烷进行区域选择性铑催化的δ-硼化，从而获得手性仲苄基硼酸酯。结果对比了γ，δ-不饱和酰胺的γ-硼化，其中双取代的烯烃部分仅带有烷基取代基。区域化学的逆转与π-面部选择性意义上的逆转相结合。
• Direct synthesis of β^2,3‐amino acid from β‐hydroxycarbamides: Implication in the synthesis of azumamide analogs and conformational analysis
  作者：Afsar Ali Khan、Jayanti Vaishnav、Manoj Kumar Gangwar、Ravi Sankar Ampapathi、Dipankar Koley

  DOI：10.1002/jhet.4717

  日期：2023.11

  The designed β2,3 unnatural amino acids have been synthesized from α-methyl-β-hydroxycarbamides via direct azidation without obtaining eliminated products. Furthermore, these β2,3 amino acids were utilized to synthesize cyclic tetrapeptides (CTPs) as azumamide analogs. 2D-NMR analysis revealed the compact secondary structure as a single conformer. Presence of intramolecular H-bonding in CTPs was observed

  所设计的β 2,3非天然氨基酸是由α-甲基-β-羟基脲通过直接叠氮化合成的，没有获得消除的产物。此外，这些 β2,3氨基酸被用来合成环状四肽（CTP）作为 azumamide 类似物。二维核磁共振分析揭示了紧凑的二级结构为单一构象异构体。在这种 α 3 β 2,3结构中观察到 CTP 中存在分子内氢键，并显示出七元 γ 转角结构。
• Versatile Asymmetric Synthesis of the Kavalactones:  First Synthesis of (+)-Kavain
  作者：Thomas E. Smith、Mabel Djang、Alan J. Velander、C. Wade Downey、Kathleen A. Carroll、Sophie van Alphen

  DOI：10.1021/ol0493960

  日期：2004.7.1

  Three asymmetric pathways to the kavalactones have been developed. The first method is chiral auxiliary-based and utilizes aldol reactions of N-acetyl thiazolidinethiones followed by a malonate displacement/decarboxylation reaction. The second approach uses the asymmetric catalytic Mukaiyama additions of dienolate nucleophile equivalents developed by Carreira and Sato. Finally, tin-substituted intermediates, prepared by either of these routes, can serve as advanced general precursors of kavalactone derivatives via Pd(0)-catalyzed Stille couplings with aryl halides.