tert-butyl((2,4-dimethylpenta-1,4-dien-3-yl)oxy)dimethylsilane | 127808-52-0

• 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: tert-butyl((2,4-dimethylpenta-1,4-dien-3-yl)oxy)dimethylsilane
• 英文别名: Tert-butyl-(2,4-dimethylpenta-1,4-dien-3-yloxy)-dimethylsilane
• CAS: 127808-52-0
• 化学式: C₁₃H₂₆OSi
• 分子量: 226.434
• InChiKey: XFLKUKXLLIVYON-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.53
• 重原子数：
  15
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  tert-butyl((2,4-dimethylpenta-1,4-dien-3-yl)oxy)dimethylsilane 在 盐酸 、 sodium hydroxide 、 1,5-cis,cis-cyclooctadiene 、 硼烷 、 双氧水 作用下， 以 四氢呋喃 为溶剂， 反应 20.0h， 生成 (2S,4S)-2,4-Dimethylpentan-1,3,5-triol
  参考文献：
  名称：

  Harada, Toshiro; Inoue, Atsushi; Wada, Isao, Journal of the American Chemical Society, 1993, vol. 115, # 17, p. 7665 - 7674

  摘要：

  DOI：
• 作为产物：
  描述：

  2,4-dimethyl-penta-1,4-dien-3-ol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 15.0h， 以96%的产率得到tert-butyl((2,4-dimethylpenta-1,4-dien-3-yl)oxy)dimethylsilane
  参考文献：
  名称：

  Harada, Toshiro; Inoue, Atsushi; Wada, Isao, Journal of the American Chemical Society, 1993, vol. 115, # 17, p. 7665 - 7674

  摘要：

  DOI：

文献信息

• Inter- and Intramolecular Differentiation of Enantiotopic Dioxane Acetals through Oxazaborolidinone-Mediated Enantioselective Ring-Cleavage Reaction:  Kinetic Resolution of Racemic 1,3-Alkanediols and Asymmetric Desymmetrization of <i>M</i><i>eso</i>-1,3-polyols
  作者：Toshiro Harada、Takayuki Egusa、Yasuto Igarashi、Motoharu Kinugasa、Akira Oku

  DOI：10.1021/jo025944g

  日期：2002.10.1

  Acetals derived from racemic 1,3-alkanediols undergo kinetic resolution in chiral oxazaborolidinone-mediated ring-cleavage reaction with nucleophiles such as enol silanes and allylic silanes. Enantioselectivity of the reaction is affected by nucleophiles, the N-sulfonyl groups of oxazaborolidinones, and the substituents attached to the acetal carbon. For disubstituted acetals rac-1 and for trisubstituted

  衍生自外消旋1,3-链烷二醇的缩醛在手性氧杂氮杂硼烷酮介导的与亲核试剂（例如烯醇硅烷和烯丙基硅烷）的环裂解反应中经历动力学拆分。反应的对映选择性受亲核试剂，草氮杂硼烷酮的N-磺酰基和与缩醛碳相连的取代基的影响。对于衍生自syn-2,4-二甲基-1,3-戊二醇的二取代乙缩醛rac-1和三取代乙缩醛rac-2，通过使用甲烯丙基硅烷7b，c作为亲核试剂与N-间甲氧杂氮杂硼硼烷酮4a结合可获得令人满意的对映选择性。 。另一方面，通过将甲硅烷基烯酮缩醛5e与N-甲苯磺酰氧杂硼硼烷酮4b组合使用，可以实现源自抗2,4-二甲基-1,3-戊二醇的三取代缩醛rac-3b的对映选择性反应。通过消旋缩醛的动力学拆分或对映异构体区分反应而优化的反应条件已成功地通过双缩醛衍生物的对位缩醛部分的分子内分化而成功用于meso-1,3-多元醇的不对称脱对称。环裂解反应作为前手性多元醇的对映选择性末端分化方法的实用性在戊醛
• Rhodium-Catalyzed Desymmetrization of meso-Glutaric Anhydrides to Access Enantioenriched anti,anti-Polypropionates
  作者：Tomislav Rovis、Brian Cochran、Daniel Henderson、Scott Thullen

  DOI：10.1055/s-0036-1591488

  日期：2018.2

  An expedient desymmetrization of 3,5-dimethyl-4-alkoxyglutaric anhydrides to access anti,anti-polypropionates is described. The previously unknown anhydrides are rapidly assembled from readily available precursors. A Rh(I)·t-BuPHOX catalyst system was found to provide good yield and high selectivities. With these conditions, the trisubstituted anhydrides were desymmetrized with various alkyl zinc reagents to provide synthetically useful enantioenriched anti,anti-2,4-dimethyl-3-hydroxy-δ-ketoacids. An identical catalyst system also affords access to syn,syn-stereotriads as well as a partial kinetic resolution of a chiral anhydride.

  描述了一种将3,5-二甲基-4-烷氧基戊二酸酐进行快速非对称化处理，以获得反-反-聚丙酸酯的方法。以前未知的酐可以从易得的前体迅速组装而成。发现Rh(I)·t-BuPHOX催化剂体系提供了良好的产率和高选择性。在这些条件下，使用各种烷基锌试剂对三取代酐进行非对称化处理，从而提供合成有用的对映富集的反-反-2,4-二甲基-3-羟基-δ-酮酸。相同的催化剂体系还可获得同-同-立体三联体，并部分进行手性酐的动力学拆分。
• Stereoselective Synthesis of the C1−C11 and C12−C34 Fragments of Mycalolide A
  作者：Thomas J. Hoffman、Amandine Kolleth、James H. Rigby、Stellios Arseniyadis、Janine Cossy

  DOI：10.1021/ol101145t

  日期：2010.8.6

  A convergent synthesis of the C1−C11 and C12−C34 fragments of mycalolide A is described. Synthetic highlights include a highly E-selective cross-metathesis between a vinyl-functionalized bis-oxazole unit and a polypropionate side chain to introduce the C19−C20 double bond and an enzymatic desymmetrization of a meso-diol in addition to five stereoselective allylations/crotylations to control the 11

  描述了Mycalolide A的C1-C11和C12-C34片段的会聚合成。合成亮点包括乙烯基官能化的双恶唑单元和聚丙烯酸酯侧链之间的高度E选择性交叉复分解，以引入C19-C20双键，以及中消旋二醇的酶促脱对称化，此外还有五个立体选择性烯丙基化/丁酸酯化以控制天然产物中存在的11个立体生成中心。
• Enantioselective total synthesis of (−)-denticulatins A and B using a novel group-selective aldolization of a meso dialdehyde as a key step
  作者：Jef De Brabander、Wolfgang Oppolzer

  DOI：10.1016/s0040-4020(97)00617-0

  日期：1997.7

  The diastereoselective synthesis of (-)-denticulatin A (1a) was achieved for the first time in 9 steps (41% yield) based on a novel group-selective aldolization of a meso dialdehyde as a key step. The inherent chirality present in bornanesultam 4 was thus transmitted to the five stereocenters spanning C-4-C-8 in key intermediate 8. In addition, denticulatin B (1b) was obtained from the common intermediate 8 en route to denticulatin A in 10 steps and 35% overall yield. (C) 1997 Elsevier Science Ltd.
• A highly convergent asymmetric synthesis of the C(19)-C(27) segment of rifamycin S: an application of enantiodifferentiating acetalization with menthone
  作者：Toshiro Harada、Yasuhiro Kagamihara、Sachi Tanaka、Kazuhiko Sakamoto、Akira Oku

  DOI：10.1021/jo00032a004

  日期：1992.3

  An enantiodifferentiating transformation of 1,3-alkanediols by kinetic acetalization with menthone is developed and used in a highly convergent asymmetric synthesis of the C(19)-C(27) segment of the ansa chain of rifamycin S.