(R)-5-(tert-butyldimethylsilyloxy)-3-methyl-2-pentanone | 175979-83-6

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (R)-5-(tert-butyldimethylsilyloxy)-3-methyl-2-pentanone
• 英文别名: (R)-4-(tert-butyldimethylsilanyloxy)-3-methylpentan-2-one；(3R)-5-[tert-butyl(dimethyl)silyl]oxy-3-methylpentan-2-one
• CAS: 175979-83-6
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: ULOUYHOAGHTVCR-SNVBAGLBSA-N

物化性质

• 沸点：
  259.4±23.0 °C(Predicted)
• 密度：
  0.865±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.62
• 重原子数：
  15
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 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)-5-(tert-butyldimethylsilyloxy)-3-methyl-2-pentanone 在 lithium aluminium tetrahydride 作用下， 以 乙醚 为溶剂， 生成 (R)-5-(tert-Butyl-dimethyl-silanyloxy)-3-methyl-pentan-2-ol
  参考文献：
  名称：

  Practical Syntheses of Enantiomerically Enriched γ-Lactones and γ-Hydroxy Ketones by the Alkylation of Pseudoephedrine Amides with Epoxides and Their Derivatives

  摘要：

  Pseudoephedrine amide enolates are shown to undergo efficient alkylation reactions with epoxides as electrophiles. Reactions with monosubstituted epoxides are subject to stereochemical matching such that the pairing leading to the 1,3-syn diastereomer is a highly selective, synthetically useful process, while the pairing forming the 1,3-anti diastereomer is not. Reactions with the 1,1-disubstituted epoxide isobutylene oxide are also highly diastereoselective and synthetically useful, but ethylene oxide exhibits poor diastereoselectivity. As an alternative to the use of ethylene oxide, 2-(tert-butyldimethylsilyloxy)ethyl iodide is shown to undergo highly diastereoselective and efficient alkylation reactions with pseudoephedrine amide enolates. Interestingly, epoxides and alkyl halides are found to attack opposite pi-faces of pseudoephedrine amide enolates. The products of each of these alkylation reactions are transformed efficiently into gamma-lactones by acidic hydrolysis and into methyl ketones by the addition of methyllithium. The methodology described provides useful procedures for the synthesis of enantiomerically enriched gamma-lactones and gamma-hydroxy ketones.

  DOI：

  10.1021/jo952032o
• 作为产物：
  描述：

  甲基锂 、 [1S(R),2S]-N-(2-hydroxy-1-methyl-2-phenylethyl)-4-(tert-butyldimethylsilyloxy)-N,2-dimethylbutanamide 以 乙醚 为溶剂， 以89%的产率得到(R)-5-(tert-butyldimethylsilyloxy)-3-methyl-2-pentanone
  参考文献：
  名称：

  Practical Syntheses of Enantiomerically Enriched γ-Lactones and γ-Hydroxy Ketones by the Alkylation of Pseudoephedrine Amides with Epoxides and Their Derivatives

  摘要：

  Pseudoephedrine amide enolates are shown to undergo efficient alkylation reactions with epoxides as electrophiles. Reactions with monosubstituted epoxides are subject to stereochemical matching such that the pairing leading to the 1,3-syn diastereomer is a highly selective, synthetically useful process, while the pairing forming the 1,3-anti diastereomer is not. Reactions with the 1,1-disubstituted epoxide isobutylene oxide are also highly diastereoselective and synthetically useful, but ethylene oxide exhibits poor diastereoselectivity. As an alternative to the use of ethylene oxide, 2-(tert-butyldimethylsilyloxy)ethyl iodide is shown to undergo highly diastereoselective and efficient alkylation reactions with pseudoephedrine amide enolates. Interestingly, epoxides and alkyl halides are found to attack opposite pi-faces of pseudoephedrine amide enolates. The products of each of these alkylation reactions are transformed efficiently into gamma-lactones by acidic hydrolysis and into methyl ketones by the addition of methyllithium. The methodology described provides useful procedures for the synthesis of enantiomerically enriched gamma-lactones and gamma-hydroxy ketones.

  DOI：

  10.1021/jo952032o

文献信息

• On the structure of the Phytophthora α1 mating hormone: synthesis and comparison of four candidate stereoisomers
  作者：Reena Bajpai、Fanglong Yang、Dennis P. Curran

  DOI：10.1016/j.tetlet.2007.09.054

  日期：2007.11

  Two two-compound mixtures of candidate structures for the Phytophthora alpha 1 mating hormone have been synthesized. The mixtures were designed to have differing configurations at C3, but proved to be identical. This suggests that epimerization occurred at C3, and comparison with the data for the natural samples suggest that this is also a mixture of isomers. (c) 2007 Elsevier Ltd. All rights reserved.
• Diversity-Oriented Synthesis of Polyketide Natural Products via Iterative Chemo- and Stereoselective Functionalization of Polyenoates:  Development of a Unified Approach for the C(1−19) Segments of Lituarines A−C
  作者：Amos B. Smith、Shawn P. Walsh、Michael Frohn、Matthew O. Duffey

  DOI：10.1021/ol047792c

  日期：2005.1.1

  A unified, stereocontrolled synthesis of the C(1-19) segments of the lituarines A-C (1-3) has been achieved, highlighted by application of an iterative chemo- and stereoselective trienoate functionalization protocol, a strategy that holds considerable promise for the diversity oriented synthesis of polyketides.
• Practical Syntheses of Enantiomerically Enriched γ-Lactones and γ-Hydroxy Ketones by the Alkylation of Pseudoephedrine Amides with Epoxides and Their Derivatives
  作者：Andrew G. Myers、Lydia McKinstry

  DOI：10.1021/jo952032o

  日期：1996.1.1

  Pseudoephedrine amide enolates are shown to undergo efficient alkylation reactions with epoxides as electrophiles. Reactions with monosubstituted epoxides are subject to stereochemical matching such that the pairing leading to the 1,3-syn diastereomer is a highly selective, synthetically useful process, while the pairing forming the 1,3-anti diastereomer is not. Reactions with the 1,1-disubstituted epoxide isobutylene oxide are also highly diastereoselective and synthetically useful, but ethylene oxide exhibits poor diastereoselectivity. As an alternative to the use of ethylene oxide, 2-(tert-butyldimethylsilyloxy)ethyl iodide is shown to undergo highly diastereoselective and efficient alkylation reactions with pseudoephedrine amide enolates. Interestingly, epoxides and alkyl halides are found to attack opposite pi-faces of pseudoephedrine amide enolates. The products of each of these alkylation reactions are transformed efficiently into gamma-lactones by acidic hydrolysis and into methyl ketones by the addition of methyllithium. The methodology described provides useful procedures for the synthesis of enantiomerically enriched gamma-lactones and gamma-hydroxy ketones.