cis-4-phenyl-3-(trimethylsilyl)oxetan-2-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: cis-4-phenyl-3-(trimethylsilyl)oxetan-2-one
• 英文别名: cis-4-phenyl-3-trimethylsilyloxetan-2-one；4-Phenyl-3-trimethylsilyloxetan-2-one；4-phenyl-3-trimethylsilyloxetan-2-one
• 化学式: C₁₂H₁₆O₂Si
• 分子量: 220.343
• InChiKey: NZTMHYPJIYOBKP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.99
• 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：

  cis-4-phenyl-3-(trimethylsilyl)oxetan-2-one 以 氘代甲苯 、 甲苯 为溶剂， 反应 2.58h， 生成 (Z)-4-phenyl-3-trimethylsilylbut-3-en-2-one
  参考文献：
  名称：

  Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones

  摘要：

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.

  DOI：

  10.1021/jo4014645
• 作为产物：
  描述：

  三甲基硅烷基乙烯酮 、 苯甲醛 在 三氟化硼乙醚 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到cis-4-phenyl-3-(trimethylsilyl)oxetan-2-one
  参考文献：
  名称：

  Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones

  摘要：

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.

  DOI：

  10.1021/jo4014645

文献信息

• Synthesis and inhibitory action on HMG-CoA synthase of racemic and optically active oxetan-2-ones (β-Lactones)
  作者：Daniel Romo、Paul H.M. Harrison、Stephen I. Jenkins、R.William Riddoch、Kaapjoo Park、Hong Woon Yang、Cunxiang Zhao、Gerard D. Wright

  DOI：10.1016/s0968-0896(98)00114-x

  日期：1998.8

  but variable enantioselectivity (22-85% ee). In in vitro assays using both native and recombinant HMG-CoA synthase from Saccharomyces cerevisiae, oxetan-2-ones mono-substituted at C4 with linear alkyl chains gave IC50s that decreased monotonically with chain length up to 10 carbons and then rose rapidly for longer chains. The trans isomers of 3-methyl-4-alkyl-oxetan-2-ones showed a similar trend but had

  研究了C3-未取代和C3-甲基取代的氧杂环丁烷-2-酮（β-内酯）的同源系列，它们是酵母3-羟基-3-甲基戊二酰辅酶A（HMG-CoA）合酶的潜在抑制剂。研究了几种报道的外消旋β-内酯合成方法，以制备目标系列。此外，研究了由Et2AlCl与（1R，2R）-2-[[（二苯基）羟甲基]环己-1-醇组合制得的新型铝基路易斯酸，用于醛和三甲基甲硅烷基烯酮的不对称[2 + 2]环加成反应。该路易斯酸显示出良好的反应性，但是对映选择性可变（22-85％ee）。在使用来自酿酒酵母的天然和重组HMG-CoA合酶进行的体外分析中，在C4处被直链烷基链单取代的氧杂环丁烷-2-酮的IC50随链长增加至10个碳原子而单调下降，然后对于更长的链迅速上升。3-甲基-4-烷基-氧杂环丁烷-2-酮的反式异构体显示出相似的趋势，但IC50降低了1.3-5.6倍。结果暗示该酶中的大量疏水口袋与氧杂环丁烷-2-酮抑制剂的C-3和C-4取代基相互作用。
• Silicon Acceleration of a Tandem Alkene Isomerization/Electrocyclic Ring-opening of 2-Methyleneoxetanes to α,β-Unsaturated Methylketones
  作者：Elisa Farber、Aleksandra Rudnitskaya、Santosh Keshipeddy、Kendricks S. Lao、José A. Gascón、Amy R. Howell

  DOI：10.1021/jo4014645

  日期：2013.11.15

  The first rearrangement of 2-methyleneoxetanes to alpha,beta-unsaturated methylketones is reported. It is proposed that when these substrates are heated, the corresponding oxetenes are formed and subsequently undergo electrocyclic ring-opening to methyl vinylketones. In particular, alpha-silyl-alpha,beta-unsaturated methylketones were isolated in moderate to high yields and with high stereoselectivities. Based on the proposed mechanism, density functional theory explains the differential kinetics and stereoselectivities among substrates.