(3R,5R)-3,5-bis(tert-butyldiphenylsilyloxymethyl)morpholine

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: (3R,5R)-3,5-bis(tert-butyldiphenylsilyloxymethyl)morpholine
• 英文别名: (3R,5R)-3,5-bis(tert-butyldiphenylsiloxymethyl)morpholine；tert-butyl-[[(3R,5R)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]morpholin-3-yl]methoxy]-diphenylsilane
• 化学式: C₃₈H₄₉NO₃Si₂
• 分子量: 623.983
• InChiKey: LMOXVSUFMGNFMD-ROJLCIKYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.5
• 重原子数：
  44
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.37
• 拓扑面积：
  39.7
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  聚合甲醛 、 (3R,5R)-3,5-bis(tert-butyldiphenylsilyloxymethyl)morpholine 在 10 wt% Pd(OH)2 on carbon 、 氢气 、 溶剂黄146 作用下， 以 甲醇 为溶剂， 反应 3.0h， 以81%的产率得到4-methyl-(3R,5R)-3,5-bis(tert-butyldiphenylsiloxymethyl)morpholine
  参考文献：
  名称：

  叔胺促进的烯酮叠氮化：影响对映选择性诱导的因素的研究

  摘要：

  通过手性叔胺促进的α，β-不饱和酮的手性叔胺促进的亲核叠氮反应，利用原位生成的N - N酰基化物（氨基胺）合成了反式N-未取代的氮丙啶（至多77％ee ）。合成并评估了多种手性叔胺，从而可以得出结构-活性关系。用几种烯酮评估了不对称叠氮化的最有效启动子奎宁，以确定底物结构对产物ee的影响，而中间肼盐则通过X射线晶体学表征。

  DOI：

  10.1016/j.tetasy.2013.11.008
• 作为产物：
  描述：

  二聚甘油 在 咪唑 、 4-二甲氨基吡啶 、 palladium dihydroxide 、 氢气 、 三乙胺 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 48.0h， 生成 (3R,5R)-3,5-bis(tert-butyldiphenylsilyloxymethyl)morpholine
  参考文献：
  名称：

  Symmetry-Assisted Synthesis of C₂-Symmetric trans-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes

  摘要：

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.

  DOI：

  10.1021/jo971995f

文献信息

• Facile Route to 3,5-Disubstituted Morpholines:  Enantioselective Synthesis of O-Protected <i>trans</i>-3,5-Bis(hydroxymethyl)morpholines
  作者：Rajesh Dave、N. André Sasaki

  DOI：10.1021/ol035998s

  日期：2004.1.1

  trans-3,5-Bis(benzyl/tert-butyldiphenylsilyloxymethyl)morpholines, promising candidates for the C-2-symmetric class of chiral reagents, were prepared with excellent optical purity. A key step in the synthesis is the coupling of a serinol derivative with 2,3-O-isopropylideneglycerol triflate or its equivalent. This methodology was extended to the synthesis of chiral trans-3-(benzyloxymethyl)-5-(tert-butyldiphenylsilyloxymethyl)morpholine, a potentially useful chiral building block.
• Symmetry-Assisted Synthesis of <i>C</i>₂-Symmetric <i>trans</i>-α,α‘-Bis(hydroxymethyl)pyrrolidine and -piperidine Derivatives via Double Sharpless Asymmetric Dihydroxylation of α,ω-Terminal Dienes
  作者：Hiroki Takahata、Seiki Takahashi、Shin-ichi Kouno、Takefumi Momose

  DOI：10.1021/jo971995f

  日期：1998.4.1

  A new strategy has been developed for the synthesis of C-2-symmetric trans-alpha,alpha'-bis(hydroxymethyl)pyrrolidine and piperidine derivatives 1-3 starting from symmetric alpha,omega-terminal dienes 4-6. The double-asymmetric dihydroxylation (AD) reaction of 4-6 gave C-2-symmetric tetrols, which were converted in a four-step sequence to C-2-symmetric azacycloalkanes 17, 9, and 22, respectively. These azacycloalkanes were transformed into 1-3 in high enantiomeric excess (82% --> 98%ee). The double AD reaction proved to cause enantiomeric enhancement, even though the asymmetric induction for the first AD reaction is moderate. In addition, it was observed that the chromatography on silica gel of several C-2-symmetric azacycloalkanes (17, 20, and 22) of varying ee's resulted in marked enantiomeric fractionation.
• Tertiary amine-promoted enone aziridination: investigations into factors influencing enantioselective induction
  作者：Alan Armstrong、Robert D.C. Pullin、Chloe R. Jenner、Klement Foo、Andrew J.P. White、James N. Scutt

  DOI：10.1016/j.tetasy.2013.11.008

  日期：2014.1

  synthesised (up to 77% ee) via a chiral tertiary amine-promoted nucleophilic aziridination of α,β-unsaturated ketones utilising in situ generated N–N ylides (aminimines). A wide range of chiral tertiary amines were synthesised and evaluated, allowing structure–activity relationships to be drawn. The most efficient promoter for asymmetric aziridination, quinine, was assessed with several enones to ascertain

  通过手性叔胺促进的α，β-不饱和酮的手性叔胺促进的亲核叠氮反应，利用原位生成的N - N酰基化物（氨基胺）合成了反式N-未取代的氮丙啶（至多77％ee ）。合成并评估了多种手性叔胺，从而可以得出结构-活性关系。用几种烯酮评估了不对称叠氮化的最有效启动子奎宁，以确定底物结构对产物ee的影响，而中间肼盐则通过X射线晶体学表征。