(3R,5R)-5-(1-(tert-butyldiphenylsilyloxy)-2-methylpropan-2-yl)-3-methyldihydrofuran-2(3H)-one | 215317-64-9

• 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: (3R,5R)-5-(1-(tert-butyldiphenylsilyloxy)-2-methylpropan-2-yl)-3-methyldihydrofuran-2(3H)-one
• 英文别名: (3R,5R)-5-(2-{[tert-butyl(diphenyl)silyl]oxy}-1,1-dimethylethyl)-3-methyldihydro-2(3H)-furanone；(3R,5R)-5-[1-[tert-butyl(diphenyl)silyl]oxy-2-methylpropan-2-yl]-3-methyloxolan-2-one
• CAS: 215317-64-9
• 化学式: C₂₅H₃₄O₃Si
• 分子量: 410.629
• InChiKey: MDMIVXIREYYSGM-DENIHFKCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.54
• 重原子数：
  29
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 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：

  (3R,5R)-5-(1-(tert-butyldiphenylsilyloxy)-2-methylpropan-2-yl)-3-methyldihydrofuran-2(3H)-one 在 吡啶 、 锂硼氢 、 草酰氯 、 三氟甲磺酸 、 四丁基氟化铵 、 二甲基亚砜 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 为溶剂， 反应 74.5h， 生成 (2R,4R)-5-formyl-4-[(p-methoxybenzyl)oxy]-2,5-dimethylhexyl pivalate
  参考文献：
  名称：

  Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga Polycavernosa tsudai

  摘要：

  A stereoselective total synthesis of natural levorotatory polycavemoside A (1) has been achieved. initial investigations produced the properly activated disaccharide unit 18b via the conjoining of building blocks originating from L-fucose and D-xylose. This objective was followed by preparation of the phenylsulfonyl-substituted tetrahydropyran 23 and aldehyde 30. After proper linking of these key compounds, important information had to be garnered on the sequence of steps that would ultimately result in successful access to 1. Although oxidation to generate alpha-diketone 35 and unmasking of the C-13 hydroxyl did give rise efficiently to lactol 36, this functionality did not pave the way for ensuring macrolactonization. When this sequence of steps was reversed, it was indeed possible to arrive at the heavily functionalized precursor 43. However, numerous experiments failed to result in the requisite activation of C-16 for attachment of the trienyl side chain. However, if the E-vinyl iodide was elaborated in advance of alpha-diketone generation, glycosidation, and complete side chain construction, arrival at 1 proceeded without unsurmountable complications to furnish the targeted marine toxin.

  DOI：

  10.1021/ja993487o
• 作为产物：
  描述：

  3-(苄氧基)-2,2-二甲基-1-丙醇 在 咪唑 、 RuCl2(1,3-dimesityl-imidazolidin-2-yl)(PCy3)(=CHPh) 、 titanium(IV) isopropylate 、 4-二甲氨基吡啶 、 草酰氯 、 18-冠醚-6 、 L-(+)-酒石酸二乙酯 、 palladium 10% on activated carbon 、 氢气 、 碘 、 双(三甲基硅烷基)氨基钾 、 二异丁基氢化铝 、 二甲基亚砜 、 三乙胺 、 三苯基膦 、 sodium iodide 、 锌 作用下， 以 四氢呋喃 、 甲醇 、 乙醚 、 二氯甲烷 、 甲苯 为溶剂， 反应 51.0h， 生成 (3R,5R)-5-(1-(tert-butyldiphenylsilyloxy)-2-methylpropan-2-yl)-3-methyldihydrofuran-2(3H)-one
  参考文献：
  名称：

  聚卡维诺糖苷A的γ-丁内酯亚基的立体选择性合成

  摘要：

  据报道，通过使用Sharpless不对称环氧化，闭环易位和非对映体选择性加氢，聚卡维诺利德A的γ-丁内酯亚基的高效，多功能线性合成具有10个线性步骤，总收率达14.2％。

  DOI：

  10.1002/jhet.3240

文献信息

• A Modular Enantioselective Approach to Construction of the Macrolactone Core of Polycavernoside A
  作者：Leo A. Paquette、Dmitri Pissarnitski、Louis Barriault

  DOI：10.1021/jo981083t

  日期：1998.10.1

  A program directed toward a total synthesis of polycavernoside A is described. The synthesis of five building blocks is detailed. The first of two electrophilic units, the lactone 3, was prepared in four steps from the known enantiomerically pure oxirane 15. Pyranyl aldehyde 5 was elaborated in turn from L-malic acid via 10. While the route to 30 involved 3 as a starting material, dithiane 2 was obtained in a straightforward manner from 10 as well. The merging of the chiral sectors could not be accomplished by way of the lithiated dithianyl anions, presumably as a consequence of their heightened basicity. The strategic incorporation of the trienyl sector was accomplished, although no attempt was made to control the diastereoselectivity of the process.
• Stereocontrolled Elaboration of Natural (−)-Polycavernoside A, a Powerfully Toxic Metabolite of the Red Alga <i>Polycavernosa</i> <i>tsudai</i>
  作者：Leo A. Paquette、Louis Barriault、Dmitri Pissarnitski、Jeffrey N. Johnston

  DOI：10.1021/ja993487o

  日期：2000.2.1

  A stereoselective total synthesis of natural levorotatory polycavemoside A (1) has been achieved. initial investigations produced the properly activated disaccharide unit 18b via the conjoining of building blocks originating from L-fucose and D-xylose. This objective was followed by preparation of the phenylsulfonyl-substituted tetrahydropyran 23 and aldehyde 30. After proper linking of these key compounds, important information had to be garnered on the sequence of steps that would ultimately result in successful access to 1. Although oxidation to generate alpha-diketone 35 and unmasking of the C-13 hydroxyl did give rise efficiently to lactol 36, this functionality did not pave the way for ensuring macrolactonization. When this sequence of steps was reversed, it was indeed possible to arrive at the heavily functionalized precursor 43. However, numerous experiments failed to result in the requisite activation of C-16 for attachment of the trienyl side chain. However, if the E-vinyl iodide was elaborated in advance of alpha-diketone generation, glycosidation, and complete side chain construction, arrival at 1 proceeded without unsurmountable complications to furnish the targeted marine toxin.
• Stereoselective Synthesis of γ-Butyrolactones Subunit of Polycavernoside A
  作者：Sudhakar Kadari、Hemasri Yerrabelly、Thirupathi Gogula、Yadaiah Goud Erukala、Jayaprakash Rao Yerrabelly、Prem Kumar Begari

  DOI：10.1002/jhet.3240

  日期：2018.8

  An efficient and versatile linear synthesis of γ‐butyrolactone subunit of polycavernolide A has been reported in 14.2% overall yield with 10 linear steps by employing Sharpless asymmetric epoxidation, ring‐closing metathesis, and diastereoface selective hydrogenation.

  据报道，通过使用Sharpless不对称环氧化，闭环易位和非对映体选择性加氢，聚卡维诺利德A的γ-丁内酯亚基的高效，多功能线性合成具有10个线性步骤，总收率达14.2％。