Silane, (1,1-dimethylethyl)dimethyl[(2-methyl-3-furanyl)methoxy]- | 125214-88-2

• 物质功能分类: 有机原料 - 有机硅化合物
• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: Silane, (1,1-dimethylethyl)dimethyl[(2-methyl-3-furanyl)methoxy]-
• 英文别名: tert-butyl-dimethyl-[(2-methylfuran-3-yl)methoxy]silane
• CAS: 125214-88-2
• 化学式: C₁₂H₂₂O₂Si
• 分子量: 226.391
• InChiKey: DNVGRMPKGHMLRG-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.11
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  22.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Silane, (1,1-dimethylethyl)dimethyl[(2-methyl-3-furanyl)methoxy]- 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 palladium 10% on activated carbon 、 氢气 、 三乙胺 、 potassium hydroxide 、 sodium t-butanolate 作用下， 以 1,4-二氧六环 、 二氯甲烷 、 水 、 乙酸乙酯 、 甲苯 、 苯 为溶剂， -78.0~75.0 ℃ 、101.33 kPa 条件下， 反应 16.75h， 生成 [(1S,7R,9S,10R)-9-methyl-4-oxo-12-oxatricyclo[7.2.1.02,7]dodec-2-en-10-yl]methyl 4-methylbenzenesulfonate
  参考文献：
  名称：

  Highly Substituted Oxabicyclic Derivatives from Furan: Synthesis of (±)-Platensimycin

  摘要：

  A stereocontrolled approach to a key platensimycin intermediate was achieved from a commercially available furylcarboxylate. Key to our approach is the highly efficient formal [4 + 3] cyclocondensation of a substituted furan with tetrabromocyclopropene along with an intramolecular gamma-alkylation to construct the final ring of the caged intermediate.

  DOI：

  10.1021/ol2005775
• 作为产物：
  描述：

  2-甲基-3-糠酸甲酯 在 咪唑 、 lithium aluminium tetrahydride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 Silane, (1,1-dimethylethyl)dimethyl[(2-methyl-3-furanyl)methoxy]-
  参考文献：
  名称：

  Highly Substituted Oxabicyclic Derivatives from Furan: Synthesis of (±)-Platensimycin

  摘要：

  A stereocontrolled approach to a key platensimycin intermediate was achieved from a commercially available furylcarboxylate. Key to our approach is the highly efficient formal [4 + 3] cyclocondensation of a substituted furan with tetrabromocyclopropene along with an intramolecular gamma-alkylation to construct the final ring of the caged intermediate.

  DOI：

  10.1021/ol2005775

文献信息

• Studies in marine cembranolide synthesis: A synthesis of 2,3,5-trisubstituted furan intermediates for lophotoxin and pukalide
  作者：Ian Paterson、Gardner Mark、Bernard J Banks

  DOI：10.1016/s0040-4020(01)81102-9

  日期：1989.1

  Pd(0)-catalysed coupling between various furyl zinc or tin compounds and vinyl iodides is demonstrated to be a versatile method for the synthesis of 2,3-dialkyl-5-alkenylfurans like 3, as potential precursors of the ring system of lophotoxin and pukalide. A possible cyclisation substrate was successfully prepared by glycol cleavage, 21 → 24, when alcohol oxidation failed.

  Pd（0）催化的各种呋喃基锌或锡化合物与乙烯基碘之间的偶联是合成2,3-二烷基-5-链烯基呋喃（如3）的一种通用方法，可作为Lophotoxin和Rn环系统的潜在前体。普卡利德。当乙醇氧化失败时，通过乙二醇裂解21 → 24成功制备了可能的环化底物。
• Synthesis of Methylene-Expanded Oxetanocin Isonucleosides in Both Enantiomeric Forms¹
  作者：Michael E. Jung、Christopher J. Nichols

  DOI：10.1021/jo971890c

  日期：1998.1.1

  We report a novel route to isonucleosides of the 'methylene-expanded' oxetanocin class, in both the D-and L-enantiomeric forms, e.g., compounds L-(+)-2a, D-(-)-2a, and L-(-)-2b, beginning with the simple, known mono-p-bromobenzyl ether 3 of the very inexpensive 2-butene-1,4-diol. Sharpless asymmetric epoxidation of 3 gave either (-) or (+)-4 depending on the chirality of the tartrate used. The p-bromobenzyl ether was used since the epoxide product is crystalline and can be recrystallized to high optical purity. Opening of the epoxide with vinylmagnesium bromide gave the 1,3-diol 5, the primary alcohol of which was protected as the silyl ether 6. Treatment of 6 with iodonium bis(sym-collidine) perchlorate afforded the desired 5-(iodomethyl)tetrahydrofuran-3-ol 8 with loss of the bromobenzyl cation in the key step in the synthetic scheme. This iodide 8 was then converted into the bis(silyloxy)-protected alcohol 15 by acetylation to give the acetate 10, displacement of iodide with acetate, hydrolysis, and selective protection of the primary alcohols. The alcohol 6 could also be converted into 15 via initial acetylation and then iodocyclization to give 10. The diol 5 could also be converted into 15 by a similar route involving bis-acetylation and iodocyclization followed by functional group transformations. The tosylate of 15 was displaced with the anion of adenine or thymidine to give, alter final desilylation, the desired isonucleosides-the D-adenosine analogue (-)-2a and the L-adenosine and thymidine analogues (+)-2a and(-)-2b. All of the stereochemistry of the final products is derived from the first step of the synthesis, namely, the Sharpless asymmetric epoxidation of 3. The biological activity of the new compounds L-(+)-2a and L-(-)-2b against HIV was determined in the anti-HIV drug-testing system of the National Cancer Institute. The adenosine analogue L-(+)-2a was inactive in this screen, while the thymidine analogue L-(-)-2b showed moderate anti-HIV activity (IC50 > 2 x 10(-4) M, EC50 = 8 x 10(-7) M, TI50 > 250).
• Studies towards the synthesis of lophotoxin and pukalide: Synthesis of the 14-membered macrocyclic core and some acyclic structural analogues
  作者：Ian Paterson、Rebecca E Brown、Christopher J Urch

  DOI：10.1016/s0040-4039(99)01119-3

  日期：1999.7

  The 14-membered macrocycle 3, an advanced intermediate in a synthetic approach to lophotoxin, was prepared from stannane 20 using an intramolecular Stille coupling. The acyclic structural analogues 6 and 7 were obtained by analogous intermolecular coupling reactions. (C) 1999 Elsevier Science Ltd. All rights reserved.
• From virtual to clinical: The discovery of PGN-1531, a novel antagonist of the prostanoid EP4 receptor
  作者：Jon Sutton、David E. Clark、Christopher Higgs、Marcel J. de Groot、Neil V. Harris、Andrea Taylor、Peter M. Lockey、Karen Maubach、Amanda Woodrooffe、Richard J. Davis、Robert A. Coleman、Kenneth L. Clark

  DOI：10.1016/j.bmcl.2014.02.068

  日期：2014.5

  In this Letter, we present the results of a hit-finding and lead optimization programme against the EP4 receptor (EP4R). In a short time period, we were able to discover five structurally diverse series of hit compounds using a combination of virtual screening methods. The most favoured hit, compound 6, was demonstrated to be a competitive antagonist of the EP4R. Compound 73 was identified following several rounds of optimization, which centred on improving both the primary EP4R affinity and selectivity against the related EP2R as well as the aqueous solubility. This work culminated in the preparation of PGN-1531, the sodium salt of 73, which showed a marked improvement in solubility (>10 mg/mL). PGN-1531 is a potent and selective antagonist at EP(4)Rs in vitro and in vivo, with the potential to alleviate the symptoms of migraine that result from cerebral vasodilatation. (C) 2014 Elsevier Ltd. All rights reserved.
• Stereodivergent Resolution of Oxabicyclic Ketones: Preparation of Key Intermediates for Platensimycin and Other Natural Products
  作者：Michael D. VanHeyst、E. Zachary Oblak、Dennis L. Wright

  DOI：10.1021/jo4017502

  日期：2013.10.18

  An improved methodology for the preparation of enantiopure oxabicyclo[3.2.1]octadienes via a stereodivergent resolution is reported. High catalyst control proximal to the oxabridged stereocenter produces readily separable diastereomers in high yield (>92%) and with excellent optical purity (>95% ee). This resolution strategy is amenable to large-scale preparations, and the utility of the resolution was further demonstrated in the asymmetric preparation of a key intermediate used in the synthesis of the antibiotic (-)-platensimycin.