(R)-4-(dimethyl(phenyl)silyl)dihydrofuran-2(3H)-one | 198758-05-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: (R)-4-(dimethyl(phenyl)silyl)dihydrofuran-2(3H)-one
• 英文别名: (R)-(+)-3-(dimethylphenylsilyl)butyrolactone；(R)-β-dimethylphenylsilyl-γ-butyrolactone；(4R)-4-[dimethyl(phenyl)silyl]oxolan-2-one
• CAS: 198758-05-3
• 化学式: C₁₂H₁₆O₂Si
• 分子量: 220.343
• InChiKey: XBIMRAOAIGNJGM-LLVKDONJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.92
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (R)-4-(dimethyl(phenyl)silyl)dihydrofuran-2(3H)-one 在 过氧乙酸 、 硫酸 、 mercury(II) diacetate 作用下， 反应 24.0h， 以50%的产率得到(R)-3-羟基-gamma-丁内酯
  参考文献：
  名称：

  (+)-Mycotrienol 和 (+)-Mycotrienin I 的全合成：不对称巴豆基硅烷键结构的应用

  摘要：

  安沙霉素抗生素 (+)-mycotrienin I (1c) 和 (+)-mycotrienol (1d) 的高度收敛不对称合成已分别通过 C9-C16 亚基 3b 和芳香族亚基 4b 的合成和偶联实现。本文描述了这项工作的完整细节，因为它说明了我们开发的手性 (E)-巴豆基硅烷键构建方法在全合成中的实用性。所有四个立体中心都是使用手性烯丙基硅烷键构建方法引入的。在亚基 3b 的合成中，C12 和 C13 立体中心是使用不对称巴豆基甲硅烷化反应生成的 α-酮二苄基缩醛 5 的。C11 立体中心随后通过螯合控制的烯丙基三甲基硅烷添加来安装，以建立抗 1,3-二醇系统。然后通过 α,β-不饱和内酯 10b 的还原开环安装 C14-C15 三取代双键。芳族亚基 4b 的选择是基于其与酰胺基苯并基的合成子等效性...

  DOI：

  10.1021/ja9743194
• 作为产物：
  描述：

  dimethyl(oxiran-2-yl)(phenyl)silane 在 potassium osmate(VI) dihydrate 、 copper(l) iodide 作用下， 以 乙醚 、 N,N-二甲基甲酰胺 为溶剂， 反应 7.66h， 生成 (R)-4-(dimethyl(phenyl)silyl)dihydrofuran-2(3H)-one
  参考文献：
  名称：

  SmI₂-Mediated Radical Cyclizations Directed by a C−Si Bond

  摘要：

  The use of a silicon stereocontrol element in cyclobutanol and cyclopentanol-forming cyclizations mediated by SmI2 results in excellent diastereocontrol. The C-Si bond in the products of cyclization provides a versatile handle for further manipulation. An asymmetric route to cyclization substrates involving copper-catalyzed silyl transfer has also been developed.

  DOI：

  10.1021/ol102278c

文献信息

• Rhodium(I)-catalyzed enantioselective 1,4-addition of nucleophilic silicon
  作者：Christian Walter、Roland Fröhlich、Martin Oestreich

  DOI：10.1016/j.tet.2009.01.111

  日期：2009.7

  rhodium(I) by means of an RhI–OH complex, enables the conjugate transfer of nucleophilic silicon onto α,β-unsaturated acceptors. Pre- or in situ formed cationic rhodium(I)–binap complexes catalyze this novel carbon–silicon bond formation with exceptional enantiocontrol, 92 to >99% ee for cyclic carbonyl and carboxyl compounds as well as >99% ee for acyclic carboxyl compounds.

  铑（I）催化的硅-硼键活化，即通过Rh I -OH络合物将硅从硼转变为铑（I），可以将亲核硅共轭转移到α，β上-不饱和受体。预制的或原位形成的阳离子铑（I）-联萘酚配合物可催化这种新型的碳-硅键形成，具有出色的对映体控制能力，环状羰基和羧基化合物的ee为92％至> 99％ee，无环羧基化合物的ee> 99％。
• NHC–Cu(i) catalysed asymmetric conjugate silyl transfer to unsaturated lactones: application in kinetic resolution
  作者：Vittorio Pace、James P. Rae、Hassan Y. Harb、David J. Procter

  DOI：10.1039/c3cc42160k

  日期：——

  The scope of the asymmetric silyl transfer to unsaturated lactones utilising a C2-symmetric NHC–Cu(I) catalyst has been established and kinetic resolutions mediated by silyl transfer have been used to prepare enantiomerically enriched anti-4,5-disubstituted 5-membered lactones. The method has been exploited in an expedient synthesis of (+)-blastmycinone.

  利用 C2 对称 NHCâCu(I) 催化剂对不饱和内酯进行不对称硅基转移的范围已经确定，并利用硅基转移介导的动力学解析制备了对映体富集的反 4,5 二取代 5 元内酯。该方法已被用于 (+)-blastmycinone 的快速合成。
• Total Synthesis of (+)-Mycotrienol and (+)-Mycotrienin I
  作者：James S. Panek、Craig E. Masse

  DOI：10.1021/jo971793j

  日期：1997.11.1
• Claisen rearrangements of enantiomerically pure C3-(acyloxy)-(E)-vinylsilanes
  作者：Michelle A. Sparks、James S. Panek

  DOI：10.1021/jo00010a046

  日期：1991.5

  The Ireland ester Claisen rearrangement of chiral (R)- and (S)-C3-(acyloxy)-(E)-vinylsilanes gives access to a wide range of alpha-chiral-beta-silyl-(E)-hexenoic acids with useful levels of diastereoselectivity for both the 2,3-syn and 2,3-anti diastereomers as illustrated in eqs 1 and 2. The vicinal diastereoselectivities for simple propionate esters rac-1b, (S)-1e, and (R)-1g can be varied from 1:12 to 16:1 (syn:anti) depending on reaction conditions. The employment of appropriately protected glycolate esters yields Claisen products with diastereoselectivities ranging from 23:1 (syn:anti), resulting from chelation control of enolate geometry, to 1:3.6 (syn:anti) via the use of a nonchelating, silicon-protecting group. The reaction of alpha-azido acetate (R)-1i is the first example of a Claisen rearrangement involving an alpha-azido ester and results in a new approach toward the asymmetric synthesis of alpha-amino acids. The assignment of relative stereochemistry based on the vicinal coupling constant data has been well documented.
• SmI₂-Mediated Radical Cyclizations Directed by a C−Si Bond
  作者：Hassan Y. Harb、Karl D. Collins、Jose V. Garcia Altur、Sue Bowker、Leonie Campbell、David J. Procter

  DOI：10.1021/ol102278c

  日期：2010.12.3

  The use of a silicon stereocontrol element in cyclobutanol and cyclopentanol-forming cyclizations mediated by SmI2 results in excellent diastereocontrol. The C-Si bond in the products of cyclization provides a versatile handle for further manipulation. An asymmetric route to cyclization substrates involving copper-catalyzed silyl transfer has also been developed.