rac-(3R,4R)-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-3-methyloxetan-2-one

• 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: rac-(3R,4R)-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-3-methyloxetan-2-one
• 英文别名: trans-(+/-)-4-(2-tert-butyldimethylsiloxyethyl)-3-methyloxetan-2-one；trans-4-(2-tert-butyldimethylsilyloxyethyl)-3-methyloxetan-2-one；(3S,4S)-4-[2-[tert-butyl(dimethyl)silyl]oxyethyl]-3-methyloxetan-2-one
• 化学式: C₁₂H₂₄O₃Si
• 分子量: 244.406
• InChiKey: LGJMFZLXWSAFIN-UWVGGRQHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.96
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  35.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  rac-(3R,4R)-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-3-methyloxetan-2-one 、 alkaline earth salt of/the/ methylsulfuric acid 以 甲苯 为溶剂， 以75%的产率得到tert-Butyl-dimethyl-[2-((2S,3S)-3-methyl-4-methylene-oxetan-2-yl)-ethoxy]-silane
  参考文献：
  名称：

  Preparation and Properties of 2-Methyleneoxetanes

  摘要：

  The methylenation of beta-lactones 5 with dimethyltitanocene provides a versatile, reliable, and highly chemoselective entry to 2-methyleneoxetanes 7. The conversion proceeds selectively in the presence of alkenes, unprotected alcohols, and a variety of other carbonyl moieties, A study of conditions for the optimization of this reaction is delineated. In addition, the first X-ray structure of a 2-methyleneoxetane, which shows its similarity to related p-lactones, is reported. Reactivity studies of 2-methyleneoxetanes are presented in which it is demonstrated that these compounds are attacked at C-4 with a nucleophile; then, subsequently, the resultant enolate reacted with an electrophile. An interesting dichotomy of reactivity was observed when methyleneoxetane 7c was treated with electrophiles. Reaction of 7c with acetic acid gave acetoxyoxetane 19. When 7c was exposed to bromine, dibromoketone 20 resulted.

  DOI：

  10.1021/jo9906072
• 作为产物：
  描述：

  3-(叔丁基-二甲基-硅烷基OXY)-丙醛 、 (E)-CH3CHC(OSi(CH3)2C(CH3)3)SC5H4N 在 zinc(II) chloride 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以51%的产率得到rac-(3R,4R)-4-(2-((tert-butyldimethylsilyl)oxy)ethyl)-3-methyloxetan-2-one
  参考文献：
  名称：

  串联Mukaiyama醛醇-内酯化（TMAL）反应的研究：对β-内酯的简洁且高度非对映选择性的途径，用于强力胰腺脂肪酶抑制剂（-）-Panclicin D的全合成

  摘要：

  基于使用硫代吡啶基甲硅烷基乙烯酮缩醛和各种醛类的串联Mukaiyama醇醛内酯化法，已开发出一种简洁且高度非对映选择性的β-内酯途径。使用这种方法合成了一种有效的胰脂肪酶抑制剂（-）-PanclicinD。描述了该方法的最近的优化和扩展，其包括乙烯酮缩醛的甲硅烷基和离去基团的变化。

  DOI：

  10.1016/s0040-4020(97)01029-6

文献信息

• Studies of the tandem Mukaiyama aldol-lactonization (TMAL) reaction: A concise and highly diastereoselective route to β-lactones applied to the total synthesis of the potent pancreatic lipase inhibitor, (−)-Panclicin D
  作者：Hong Woon Yang、Cunxiang Zhao、Daniel Romo

  DOI：10.1016/s0040-4020(97)01029-6

  日期：1997.12

  A concise and highly diastereoselective route to β-lactones has been developed based on a tandem Mukaiyama aldol-lactonization employing thiopyridylsilylketene acetals and various aldehydes. (−)-Panclicin D, a potent pancreatic lipase inhibitor, was synthesized using this methodology. Recent optimization and extensions of this method are described which include variation of the silyl group and leaving

  基于使用硫代吡啶基甲硅烷基乙烯酮缩醛和各种醛类的串联Mukaiyama醇醛内酯化法，已开发出一种简洁且高度非对映选择性的β-内酯途径。使用这种方法合成了一种有效的胰脂肪酶抑制剂（-）-PanclicinD。描述了该方法的最近的优化和扩展，其包括乙烯酮缩醛的甲硅烷基和离去基团的变化。
• Carbonylation of <i>cis</i>-Disubstituted Epoxides to <i>trans</i>-β-Lactones: Catalysts Displaying Steric and Contrasteric Regioselectivity
  作者：Michael Mulzer、Geoffrey W. Coates

  DOI：10.1021/jo501899e

  日期：2014.12.19

  trans-beta-Lactones are a versatile and useful class of compounds, but reliable methods for their direct synthesis are still limited. Addressing this problem, we present herein two catalysts for the regioselective carbonylation of cis-disubstituted epoxides. The two catalysts show high activities and opposing regioselectivities so that either one of the two possible beta-lactone regioisomers can be obtained selectively.
• A Highly Diastereoselective, Tandem Mukaiyama Aldol-Lactonization Route to β-Lactones:  Application to a Concise Synthesis of the Potent Pancreatic Lipase Inhibitor, (−)-Panclicin D
  作者：Hong Woon Yang、Daniel Romo

  DOI：10.1021/jo9619488

  日期：1997.1.1
• Preparation and Properties of 2-Methyleneoxetanes
  作者：Lisa M. Dollinger、Albert J. Ndakala、Mehrnoosh Hashemzadeh、Gan Wang、Ying Wang、Isamir Martinez、Joel T. Arcari、David J. Galluzzo、Amy R. Howell、Arnold L. Rheingold、Joshua S. Figuero

  DOI：10.1021/jo9906072

  日期：1999.9.1

  The methylenation of beta-lactones 5 with dimethyltitanocene provides a versatile, reliable, and highly chemoselective entry to 2-methyleneoxetanes 7. The conversion proceeds selectively in the presence of alkenes, unprotected alcohols, and a variety of other carbonyl moieties, A study of conditions for the optimization of this reaction is delineated. In addition, the first X-ray structure of a 2-methyleneoxetane, which shows its similarity to related p-lactones, is reported. Reactivity studies of 2-methyleneoxetanes are presented in which it is demonstrated that these compounds are attacked at C-4 with a nucleophile; then, subsequently, the resultant enolate reacted with an electrophile. An interesting dichotomy of reactivity was observed when methyleneoxetane 7c was treated with electrophiles. Reaction of 7c with acetic acid gave acetoxyoxetane 19. When 7c was exposed to bromine, dibromoketone 20 resulted.