(3R,5S,6S)-6-{(1S)-2-[(tert-butyldimethylsilyl)oxy]-1-methylethyl}-3,5-dimethyltetrahydro-2H-pyran-2-one | 71828-89-2

• 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,5S,6S)-6-{(1S)-2-[(tert-butyldimethylsilyl)oxy]-1-methylethyl}-3,5-dimethyltetrahydro-2H-pyran-2-one
• 英文别名: (3R,5S,6S)-6-((S)-1-((tert-butyldimethylsilyl)oxy)propan-2-yl)-3,5-dimethyltetrahydro-2H-pyran-2-one；(3R,5S,6S)-6-[(2S)-1-[tert-butyl(dimethyl)silyl]oxypropan-2-yl]-3,5-dimethyloxan-2-one
• CAS: 71828-89-2
• 化学式: C₁₆H₃₂O₃Si
• 分子量: 300.514
• InChiKey: WYAMGGGZNAAMJI-CRWXNKLISA-N

物化性质

• 沸点：
  353.2±15.0 °C(Predicted)
• 密度：
  0.918±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.23
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.94
• 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,5S,6S)-6-{(1S)-2-[(tert-butyldimethylsilyl)oxy]-1-methylethyl}-3,5-dimethyltetrahydro-2H-pyran-2-one 在 lithium aluminium tetrahydride 、 camphor-10-sulfonic acid 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 34.0h， 生成 (2R,4S)-4-[(2'R,4'S,5'S)-2'-(4-methoxyphenyl)-5'-methyl-1',3'-dioxan-4-yl]-2-methylpentan-1-ol
  参考文献：
  名称：

  Total Synthesis of 10-Deoxymethynolide, the Aglycon of the Macrolide Antibiotic 10-Deoxymethymycin

  摘要：

  A short and efficient total synthesis of 10-deoxymethynolide (2c), the aglycon of 10-deoxymethymycin (1c), has been accomplished in 16 steps and 12% overall yield from (S)-3-O-p-toluenesulfonyl-3-hydroxy-2-methylpropanal (15c). The synthesis features an expeditious preparation of (+)-5a, a synthetic equivalent of the Prelog-Djerassi lactonic acid, and the construction of a 12-membered lactone through an intramolecular Nozaki-Hiyama-Kishi coupling reaction.

  DOI：

  10.1021/jo9809433
• 作为产物：
  描述：

  (2S,3R,4S)-5-benzyloxy-2,3-dimethylpentane-1,4-diol 在 palladium on activated charcoal 4-二甲氨基吡啶 、 potassium tert-butylate 、 氢气 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 25.0 ℃ 、303.98 kPa 条件下， 反应 12.5h， 生成 (3R,5S,6S)-6-{(1S)-2-[(tert-butyldimethylsilyl)oxy]-1-methylethyl}-3,5-dimethyltetrahydro-2H-pyran-2-one
  参考文献：
  名称：

  Total Synthesis of 10-Deoxymethynolide, the Aglycon of the Macrolide Antibiotic 10-Deoxymethymycin

  摘要：

  A short and efficient total synthesis of 10-deoxymethynolide (2c), the aglycon of 10-deoxymethymycin (1c), has been accomplished in 16 steps and 12% overall yield from (S)-3-O-p-toluenesulfonyl-3-hydroxy-2-methylpropanal (15c). The synthesis features an expeditious preparation of (+)-5a, a synthetic equivalent of the Prelog-Djerassi lactonic acid, and the construction of a 12-membered lactone through an intramolecular Nozaki-Hiyama-Kishi coupling reaction.

  DOI：

  10.1021/jo9809433

文献信息

• Stereoselective total synthesis of lysocellin, the representative polyether antibiotic of the lysocellin family. Part 1. Synthesis of C1–C9 and C16–C23 subunits
  作者：Kiyoshi Horita、Takayuki Inoue、Kazuhiro Tanaka、Osamu Yonemitsu

  DOI：10.1016/0040-4020(95)00905-1

  日期：1996.1

  The C1–C9 (4) and C16–C23 subunits (9) of lysocellin (1), a representative polyether antibiotic, were synthesized stereoselectively from D-glucose and D-mannitol. Stereocontrolled hydroboration, Michael reaction, Grignard reaction, etc. were successfully applied.

  溶血素（1）（一种代表性的聚醚抗生素）的C1-C9（4）和C16-C23亚基（9）是由D-葡萄糖和D-甘露糖醇立体选择性合成的。立体控制的硼氢化反应，迈克尔反应，格氏反应等已成功应用。
• Total synthesis of the polyether antibiotic lysocellin. 1. Stereocontrolled synthesis of the C1-C9 and C16-C23 fragments
  作者：Kiyoshi Horita、Takayuki Inoue、Kazuhiro Tanaka、Osamu Yonemitsu

  DOI：10.1016/s0040-4039(00)61139-5

  日期：1992.9

  Stereocontrolled synthesis of two fragments corresponding to the C1-C9 (3) and C16-C23 parts (6) of lysocellin (1) using hydroboration, Wittig-Homer reaction, and Michael reaction in the key steps is described.

  描述了在关键步骤中使用氢硼化，Wittig-Homer反应和Michael反应进行立体控制的两个片段，分别对应于溶菌素（1）的C 1 -C 9（3）和C 16 -C 23部分（6）。
• Formal Total Synthesis of (+)-Methynolide
  作者：Janine Cossy、David Bauer、Véronique Bellosta

  DOI：10.1055/s-2002-25364

  日期：——

  A convergent total synthesis of (+)-methynolide was achieved in 23 steps highlighted by a ring-closing metathesis, a Takai reaction, a Sharpless kinetic resolution of an allylic alcohol and a crotylboration.

  通过闭环偏析、Takai 反应、烯丙基醇的 Sharpless 动力解析和羰基硼化等 23 个步骤，实现了 (+)-methynolide 的聚合全合成。
• Total synthesis of (+)-methynolide using a Ti-mediated aldol reaction of a lactyl-bearing oxazolidin-2-one, and a vinylogous Mukaiyama aldol reaction
  作者：Takahiro Suzuki、Masataka Fujimura、Kazuhiro Fujita、Susumu Kobayashi

  DOI：10.1016/j.tet.2017.03.093

  日期：2017.6

  A highly convergent total synthesis of (+)-methynolide, based on two types of stereoselective aldol reaction, was achieved. The C1-C8 and C9-C11 fragments of (+)-methynolide were prepared by a vinylogous Mukaiyama aldol reaction using a vinyl ketene silyl N,O-acetal, and a Ti-mediated aldol reaction of a lactyl-bearing chiral oxazolidin-2-one, respectively. Yamaguchi esterification of both fragments

  基于两种类型的立体选择性醛醇缩合反应，实现了高度收敛的（+）-甲氰胺的全合成。（+）-甲氰胺的C1-C8和C9-C11片段是通过乙烯基乙烯酮甲硅烷基N，O-乙缩醛与Mukaiyama醛醇缩醛反应和含乳酸的手性恶唑烷二酮2的Ti介导的醛醇缩合反应制备的。 -一个。片段的山口酯化和闭环复分解均提供了（+）-甲氰胺。
• Acyclic stereoselection via cyclic hydroboration. Synthesis of the Prelog-Djerassi lactonic acid.
  作者：W.Clark Still、Kenneth R. Shaw

  DOI：10.1016/s0040-4039(01)82004-9

  日期：1981.1

  An intramolecularly directed hydroboration (4→5) provides high asymmetric induction for the construction of 1.

  分子内定向硼氢化（4→5）为1的构建提供了高度的不对称诱导。