(2-(3,5-dimethylphenyl)allyl)trimethylsilane | 1134593-21-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2-(3,5-dimethylphenyl)allyl)trimethylsilane
• CAS: 1134593-21-7
• 化学式: C₁₄H₂₂Si
• 分子量: 218.414
• InChiKey: AXZUYGPNYWIUBV-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.65
• 重原子数：
  15.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  (2-(3,5-dimethylphenyl)allyl)trimethylsilane 、 在 C₃₇H₃₂P₂Se₂⁽²⁺⁾*2Cl₄Ga^(1-) 作用下， 以 1,2-二氯乙烷 为溶剂， 以79 %的产率得到ethyl (6aR,8R,9S,11aR)-8-(2-(3,5-dimethylphenyl)allyl)-2,2,4,4-tetraisopropyl-11-oxohexahydro-6H-oxepino[3,2-f][1,3,5,2,4]trioxadisilocine-9-carboxylate
  参考文献：
  名称：

  Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

  摘要：

  The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged as a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility of a phosphonochalcogenide (PCH) catalyst to facilitate access into the challenging, but biologically interesting 7‐membered ring α,α’‐C‐disubstituted oxepane core through an α‐selective strain‐release C‐glycosylation. Methodically, this strategy represents a switch from more common but entropically less desired macrocyclizations to a thermodynamically favored ring‐expansion approach. In light of the general lack of stereoselective methods to access C‐septanosides, a remarkable palette of silyl‐based nucleophiles can be reliably employed in our method. This include a broad variety of useful synthons, such as easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐ketene acetal, silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that a mechanistic shift towards an intramolecular aglycone transposition involving a pentacoordinate silicon intermediate is likely responsible in steering the stereoselectivity.

  DOI：

  10.1002/anie.202405706
• 作为产物：
  描述：

  3,5-二甲基苯酚 在 吡啶 、 1,1'-双(二苯基膦)二茂铁 、 palladium diacetate 、 三乙胺 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 22.0h， 生成 (2-(3,5-dimethylphenyl)allyl)trimethylsilane
  参考文献：
  名称：

  Stereoselective Entry into α,α’‐C‐Oxepane Scaffolds through a Chalcogen Bonding Catalyzed Strain‐Release C‐Septanosylation Strategy

  摘要：

  The utility of unconventional noncovalent interactions (NCIs) such as chalcogen bonding has lately emerged as a robust platform to access synthetically difficult glycosides stereoselectively. Herein, we disclose the versatility of a phosphonochalcogenide (PCH) catalyst to facilitate access into the challenging, but biologically interesting 7‐membered ring α,α’‐C‐disubstituted oxepane core through an α‐selective strain‐release C‐glycosylation. Methodically, this strategy represents a switch from more common but entropically less desired macrocyclizations to a thermodynamically favored ring‐expansion approach. In light of the general lack of stereoselective methods to access C‐septanosides, a remarkable palette of silyl‐based nucleophiles can be reliably employed in our method. This include a broad variety of useful synthons, such as easily available silyl‐allyl, silyl‐enol ether, silyl‐ketene acetal, vinylogous silyl‐ketene acetal, silyl‐alkyne and silylazide reagents. Mechanistic investigations suggest that a mechanistic shift towards an intramolecular aglycone transposition involving a pentacoordinate silicon intermediate is likely responsible in steering the stereoselectivity.

  DOI：

  10.1002/anie.202405706

文献信息

• Gold-catalyzed synthesis of 1,3-disubstituted benzenes through tandem allylation/cyclization reaction of alkynals
  作者：Sabyasachi Bhunia、Shariar Md. Abu Sohel、Chao-Chin Yang、Shie-Fu Lush、Fwu-Ming Shen、Rai-Shung Liu

  DOI：10.1016/j.jorganchem.2008.10.049

  日期：2009.2

  Treatment of alkynals with 2-substituted allylsilanes and PPh3AuCl/AgOTf (5/3 mol%) catalyst led to formation of 1,3-disubstituted benzenes efficiently. This reaction sequence comprises an initial allylation of aldehyde, followed by cycloisomerization of enynes; PPh3AuOTf is active in both steps.

  用2-取代的烯丙基硅烷和PPh 3 AuCl / AgOTf（5/3 mol％）催化剂处理炔烃可有效地形成1,3-二取代的苯。该反应顺序包括醛的初始烯丙基化，然后是烯炔的环异构化。PPh 3 AuOTf在两个步骤中均处于活动状态。
• A Stereoselective Reductive Hosomi–Sakurai Reaction
  作者：Adriano Bauer、Nuno Maulide

  DOI：10.1021/acs.orglett.8b00276

  日期：2018.3.2

  reaction is reported. This transformation hinges on a redox-neutral, stereoselective internal reduction event under mild conditions. This operationally simple reaction relies on readily available starting materials and leads to useful products in diastereoselectivities of up to 7:1. The versatility of this new method is demonstrated through the stereoselective one-step synthesis of an AChE inhibitor.

  据报道，经典的Hosomi-Sakurai反应具有新颖的还原性。这种转变取决于在温和条件下的氧化还原中性，立体选择性内部还原事件。该操作简单的反应依赖于容易获得的起始原料，并以高达7：1的非对映选择性得到有用的产物。通过AChE抑制剂的立体选择性一步合成证明了这种新方法的多功能性。