trimethyl(2-(naphthalen-1-yl)allyl)silane | 120825-03-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: trimethyl(2-(naphthalen-1-yl)allyl)silane
• 英文别名: Trimethyl(2-naphthalen-1-ylprop-2-enyl)silane
• CAS: 120825-03-8
• 化学式: C₁₆H₂₀Si
• 分子量: 240.42
• InChiKey: KRAKTGCQSCPNSC-UHFFFAOYSA-N

物化性质

• 沸点：
  329.3±11.0 °C(Predicted)
• 密度：
  0.944±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.19
• 重原子数：
  17
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

反应信息

• 作为反应物：
  描述：

  trimethyl(2-(naphthalen-1-yl)allyl)silane 、 在 C₃₇H₃₂P₂Se₂⁽²⁺⁾*2Cl₄Ga^(1-) 作用下， 以 1,2-二氯乙烷 为溶剂， 以70 %的产率得到ethyl (6aR,8R,9S,11aR)-2,2,4,4-tetraisopropyl-8-(2-(naphthalen-1-yl)allyl)-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：

  萘酚 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 trimethyl(2-(naphthalen-1-yl)allyl)silane
  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

• Nickel catalyzed dealkoxylative C_sp2–C_sp3 cross coupling reactions – stereospecific synthesis of allylsilanes from enol ethers
  作者：Lin Guo、Matthias Leiendecker、Chien-Chi Hsiao、Christoph Baumann、Magnus Rueping

  DOI：10.1039/c4cc08187k

  日期：——

  The application of cyclic and acyclic enol ethers as electrophiles in cross coupling reactions offers new possibilities for the preparation of functional compounds.

  环状和非环状烯醇醚作为亲电试剂在交叉偶联反应中的应用为功能化合物的制备提供了新的可能性。
• Nickel-catalysed coupling of dithioacetals with silylmethylmagnesium chloride. A simple synthesis of allylsilanes
  作者：Zhi-Jie Ni、Tien-Yau Luh

  DOI：10.1039/c39880001011

  日期：——

  Allylsilanes are conveniently synthesized from the reaction of dithioacetals of ketones with trimethylsilylmethylmagnesium chloride.

  烯丙基硅烷是由酮的二硫缩醛与三甲基甲硅烷基甲基镁氯化物的反应方便地合成的。
• Development of a reductive Hosomi-Sakurai reaction
  作者：Adriano Bauer、Nuno Maulide

  DOI：10.1016/j.tet.2018.10.033

  日期：2018.11

  Herein we present a full account on the reductive Hosomi-Sakurai reaction along with some insight into the reaction mechanism. Stereoselectivity appears to be highest when the crucial carbocation intermediate, derived by protonation of the homoallylic ether, is sufficiently stabilized to ensure that the hydride transfer becomes rate-determining. This hypothesis is supported by experiment and mechanistic

  在本文中，我们对还原性细小樱井反应进行了全面介绍，并对反应机理进行了深入了解。当通过均烯丙基醚的质子化作用衍生的关键碳正离子中间体足够稳定以确保氢化物转移成为速率决定性化合物时，立体选择性似乎最高。该假设得到实验和机理分析的支持。
• Trityl Cation-Catalyzed Hosomi-Sakurai Reaction of Allylsilane with β,γ-Unsaturated α-Ketoester to Form γ,γ-Disubstituted α-Ketoesters
  作者：Zubao Gan、Deyun Cui、Hongyun Zhang、Ying Feng、Liying Huang、Yingying Gui、Lu Gao、Zhenlei Song

  DOI：10.3390/molecules27154730

  日期：——

  (Ph3C)[BPh(F)4]-catalyzed Hosomi-Sakurai allylation of allylsilanes with β,γ-unsaturated α-ketoesters has been developed to give γ,γ-disubstituted α-ketoesters in high yields with excellent chemoselectivity. Preliminary mechanistic studies suggest that trityl cation dominates the catalysis, while the silyl cation plays a minor role.

  (Ph 3 C)[BPh( F ) 4 ]-催化的 Hosomi-Sakurai 烯丙基硅烷与 β,γ-不饱和 α-酮酯的烯丙基化反应以高产率和优异的化学选择性得到 γ,γ-二取代的 α-酮酯。初步机理研究表明，三苯甲基阳离子在催化作用中起主导作用，而甲硅烷基阳离子起次要作用。
• Highly Regioselective Palladium-Catalyzed Internal Arylation of Allyltrimethylsilane with Aryl Triflates
  作者：Kristofer Olofsson、Mats Larhed、Anders Hallberg

  DOI：10.1021/jo980249n

  日期：1998.7.1

  Highly regioselective ligand-controlled Heck-arylation reactions of allyltrimethylsilane, delivering branched beta-products, were performed in moderate to good yields. The high preference for internal over terminal double-bond arylation suggests a contribution from the beta-cation-stabilizing effect of silicon. Microwave-promoted palladium-catalyzed coupling reactions proceeded with the same regioselectivity in six entries out of eight with the reaction times cut sharply down to 5-10 min.