[(S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,5,7,8-tetramethyl-chroman-2-yl]-methanol | 188416-13-9

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并吡喃
• 英文名称: [(S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,5,7,8-tetramethyl-chroman-2-yl]-methanol
• CAS: 188416-13-9
• 化学式: C₂₀H₃₄O₃Si
• 分子量: 350.574
• InChiKey: KAGOPTSULYPVCD-FQEVSTJZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.07
• 重原子数：
  24.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  38.69
• 氢给体数：
  1.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  [(S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,5,7,8-tetramethyl-chroman-2-yl]-methanol 在 吡啶 、 正丁基锂 、 [1,3-双(二苯基膦基)丙烷]二氯化钯(II) 、 三乙基硼氢化锂 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 正己烷 、 二氯甲烷 为溶剂， 反应 30.0h， 生成 tert-butyldimethyl(((R)-2,5,7,8-tetramethyl-2-((3E,7E)-4,8,12-trimethyltrideca-3,7,11-trienyl)chroman-6-yl)oxy)silane
  参考文献：
  名称：

  [EN] SYNTHESIS OF TOCOTRIENOLS FROM O-CRESOL DERIVATIVES
  [FR] SYNTHÈSE DE TOCOTRIÉNOLS À PARTIR DE DÉRIVÉS DE O-CRÉSOL

  摘要：

  本发明提供了一种环境友好、简便的工艺，用于从商业上可获得的邻甲酚衍生物制备生育三烯酚。

  公开号：

  WO2019053605A1
• 作为产物：
  描述：

  (S)-methyl 6-(tert-butyldimethylsilyloxy)-2,5,7,8-tetramethylchroman-2-carboxylate 在 二异丁基氢化铝 作用下， 生成 [(S)-6-(tert-Butyl-dimethyl-silanyloxy)-2,5,7,8-tetramethyl-chroman-2-yl]-methanol
  参考文献：
  名称：

  Synthesis of α-tocohexaenol (α-T6) a fluorescent, oxidatively sensitive polyene analogue of α-tocopherol

  摘要：

  A polyunsaturated analogue of alpha-tocopherol was synthesized that is both fluorescent and sensitive to peroxidative chemistry that occurs in phospholipid membranes. alpha-Tocohexaenol 1, [(S)-2,5,7,8-tetramethyl-2-((1E/Z,3E,5E,7E,9E)-4,8,12-trimethyltrideca-1,3,5,7,9,11-hexaenyl)chroman-6-ol, alpha-T6] was prepared by condensing a known triene fragment triphenyl-(2,6-dimethyl-octa-2,4,6-trienoic acid methyl ester)-phosphonium bromide with a protected chromanol aldehyde, (2S)-6-{[tert-butyl(dimethyl) silyl]oxy}-2,5,7,8-tetra-methyl-3,4-dihydro-2H-chromene-2-carbaldehyde. The full side chain was then completed with isopentyl(tri-n-butyl) phosphonium bromide to give 1. The geometry of the C1' - C2' alkene appears to be Z (cis) although the coupling constants of the olefinic protons are intermediate between values normally assigned to E and Z-isomers. In ethanol, alpha-T6 has a maximum absorption at 368 nm with an absorption coefficient of 45,000 M-1 cm(-1), and displays a maximum fluorescence emission at 523 nm. The susceptibility of alpha-T6 to peroxidative chemistry was dependent on the concentration of azo-initiators of lipid oxidation in acetonitrile solution as well as in phospholipid vesicles. A loss of fluorescence at 520 nm was observed when alpha-T6 ( vesicles or alpha-T6-lipid mixtures) was exposed to peroxidative conditions, and this loss mirrored the production of conjugated dienes and trienes during the peroxidation of bulk phospholipids. Addition of natural alpha-tocopherol during the AMVN induced oxidation of 4 mu M alpha-T6 and 0.5 mg/ml soybean PC induced a characteristic lag phase, after which the fluorescence of alpha-T6 began to lessen. Thus, alpha-T6 may be a useful reporter not only of tocopherol location in cells, but also of the extent of peroxidative events. (C) 2009 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.bmc.2009.11.051

文献信息

• A kinetic resolution route to the (S)-chromanmethanol intermediate for synthesis of the natural tocols
  作者：John A. Hyatt、Chad Skelton

  DOI：10.1016/s0957-4166(97)00020-7

  日期：1997.2

  Kinetic resolution of 2-hydroxymethyl-2,5,7,8-tetramethyl-6-chromanol was carried out by reaction with succinic anhydride catalysed by Amano PS-30 lipase. The (S)-enantiomer (which corresponds to the natural (2R)-configuration of the natural tocopherols and tocotrienols) was selectively acylated. An enantiomeric excess of 96.5% was achieved, and the absolute configuration was proven by conversion to known tocol intermediates. This work provides an example of the uncommon kinetic resolution of a primary neopentyl-type alcohol and provides a high-yield, chromatography-free route to a useful tocol intermediate. (C) 1997 Elsevier Science Ltd.