(2S,3R)-(E)-Methyl 3-(dimethylphenylsilyl)-2-hydroxy-hex-4-enoate | 146962-07-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (2S,3R)-(E)-Methyl 3-(dimethylphenylsilyl)-2-hydroxy-hex-4-enoate
• 英文别名: (2S,3R)-(E)-Methyl 2-hydroxy-3-(dimethylphenylsilyl)hex-4-enoate；methyl (E,2S,3R)-3-[dimethyl(phenyl)silyl]-2-hydroxyhex-4-enoate
• CAS: 146962-07-4
• 化学式: C₁₅H₂₂O₃Si
• 分子量: 278.423
• InChiKey: SLXKXBWTTCGYSY-KEGUIYOVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.08
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2S,3R)-(E)-Methyl 3-(dimethylphenylsilyl)-2-hydroxy-hex-4-enoate 在 双(乙腈)氯化钯(II) 、 三氟甲磺酸三甲基硅酯 4-二甲氨基吡啶 、 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 42.0h， 生成 (E)-(4S,5S,6R)-Methyl 4-acetoxy-6-methoxy-5-methyl-6-phenylhex-3-enoate
  参考文献：
  名称：

  Sequential diastereoselective addition and palladium(II)-catalyzed allylic acetate transposition of syn- and anti-.alpha.-acetoxy-.beta.-silyl-(E)-hex-4-enoates with achiral acetals. Asymmetric synthesis of differentiated syn and anti 1,3-diol synthons

  摘要：

  syn- and anti-methyl alpha-acetoxy-beta-(dimethylphenylsilyl)-(E)-hex-4-enoates, (2R,3R)-8a and (2S,3R)-8b, undergo highly diastereo- and enantioselective addition reactions with aldehydes and acetals 11 catalyzed by the action of trimethylsilyl trifluoromethanesulfonate (TMSOTf) generating alpha-acetoxy-beta,-gamma-unsaturated esters (allylic acetates) 12. A subsequent allylic acetate transposition promoted by dichloropalladium bisacetonitrile complex, PdCl2(MeCN)2 afforded the differentiated 1,3-diol synthons 13.

  DOI：

  10.1021/jo00057a008
• 作为产物：
  描述：

  (R)-4-(dimethyl(phenyl)silyl)-but-3-yn-2-yl acetate 在 palladium on calcium fluoride poisoned with lead 喹啉 、 4-二甲氨基吡啶 、 lithium aluminium tetrahydride 、 三甲基氯硅烷 、 氯化亚砜 、 氢气 、 N,N'-二环己基碳二亚胺 、 lithium hexamethyldisilazane 作用下， 以 乙醚 、 二氯甲烷 、 正戊烷 为溶剂， -78.0~25.0 ℃ 、101.33 kPa 条件下， 反应 36.25h， 生成 (2S,3R)-(E)-Methyl 3-(dimethylphenylsilyl)-2-hydroxy-hex-4-enoate
  参考文献：
  名称：

  Ireland-Claisen rearrangements of chiral (Z)-vinylsilanes. Highly diastereoselective synthesis of anti-.alpha.-alkoxy-.beta.-(dimethylphenylsilyl)-(E)-hex-4-enoates

  摘要：

  DOI：

  10.1021/jo00041a055

文献信息

• Vinylogous Aldol Products from Chiral Crotylsilanes Obtained by Enantioselective Rh(II) and Cu(I) Carbenoid Si−H Insertion
  作者：Jie Wu、Yu Chen、James S. Panek

  DOI：10.1021/ol100604m

  日期：2010.5.7

  Enantioenriched homoallylic ethers containing a alpha,beta-unsaturated ester (syn-vinylogous aldol products) were directly accessed by Lewis acid catalyzed crotylation utilizing chiral silane 2. The reagents were prepared by enantioselective Si-H Insertion to an alpha-diazovinylacetates using Davies' Rh-2(DOSP)(4) catalyst or chiral Cu(I) Schiff base complex.
• Ireland-Claisen rearrangements of chiral (Z)-vinylsilanes. Highly diastereoselective synthesis of anti-.alpha.-alkoxy-.beta.-(dimethylphenylsilyl)-(E)-hex-4-enoates
  作者：James S. Panek、Thomas D. Clark

  DOI：10.1021/jo00041a055

  日期：1992.7
• Sequential diastereoselective addition and palladium(II)-catalyzed allylic acetate transposition of syn- and anti-.alpha.-acetoxy-.beta.-silyl-(E)-hex-4-enoates with achiral acetals. Asymmetric synthesis of differentiated syn and anti 1,3-diol synthons
  作者：James S. Panek、Michael Yang、Jason S. Solomon

  DOI：10.1021/jo00057a008

  日期：1993.2

  syn- and anti-methyl alpha-acetoxy-beta-(dimethylphenylsilyl)-(E)-hex-4-enoates, (2R,3R)-8a and (2S,3R)-8b, undergo highly diastereo- and enantioselective addition reactions with aldehydes and acetals 11 catalyzed by the action of trimethylsilyl trifluoromethanesulfonate (TMSOTf) generating alpha-acetoxy-beta,-gamma-unsaturated esters (allylic acetates) 12. A subsequent allylic acetate transposition promoted by dichloropalladium bisacetonitrile complex, PdCl2(MeCN)2 afforded the differentiated 1,3-diol synthons 13.