1-[甲基(二苯基)甲硅烷基]丙烷-1-酮 | 86176-61-6

• 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
• 中文名称: 1-[甲基(二苯基)甲硅烷基]丙烷-1-酮
• 英文名称: 1-(methyldiphenylsilyl)-1-propanone
• 英文别名: Silane, methyl(1-oxopropyl)diphenyl-；1-[methyl(diphenyl)silyl]propan-1-one
• CAS: 86176-61-6
• 化学式: C₁₆H₁₈OSi
• 分子量: 254.404
• InChiKey: JQKVYCJYHQVFES-UHFFFAOYSA-N

物化性质

• 沸点：
  325.9±15.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 重原子数：
  18
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-[甲基(二苯基)甲硅烷基]丙烷-1-酮 在 amberlyst-15 resin 、 水 、 4-甲基苯磺酸吡啶 、 lithium diisopropyl amide 作用下， 以 丙酮 为溶剂， 反应 5.0h， 生成 (2-Methyl-1,5-dioxopentyl)methyldiphenylsilane
  参考文献：
  名称：

  Regioselectivity in [3 + 4] and [3 + 5] Annulation Reactions of Bis(trimethylsilyl) Enol Ethers with Acylsilane Dicarbonyl Dielectrophiles

  摘要：

  A number of 1,4- and 1,5-acylsilane dicarbonyl compounds were synthesized using Corey-Brook dithiane methods. These dicarbonyl substrates were annulated with the bis(trimethylsilyl) enol ether of methyl acetoacetate in the presence of TMSOTf, affording bicyclic ethers bearing silicon substituted at the bridgehead position: The annulation reactions proceeded with excellent regiochemical and good to excellent stereochemical control via a neighboring group participation mechanism. The silicon substituent was subsequently removed by treatment with fluoride ion. The overall transformation of annulation and desilylation represents a formal inversion of the regioselectivity normally exhibited with keto aldehyde dielectrophilic substrates in this process.

  DOI：

  10.1021/jo00106a025
• 作为产物：
  描述：

  甲基二苯基氯硅烷 在 正丁基锂 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.83h， 生成 1-[甲基(二苯基)甲硅烷基]丙烷-1-酮
  参考文献：
  名称：

  通过对二硅烷基烷基铜化合物的好氧氧化，可轻松合成酰基硅烷。

  摘要：

  DOI：

  10.1021/ja016716r

文献信息

• Preparation and Reactivity of Acyclic Chiral Allylzinc Species by a Zinc‐Brook Rearrangement
  作者：Markus Leibeling、Khriesto A. Shurrush、Veronika Werner、Lionel Perrin、Ilan Marek

  DOI：10.1002/anie.201602393

  日期：2016.5.10

  The zinc‐Brook rearrangement of enantiomerically enriched α‐hydroxy allylsilane produces a chiral allylzinc intermediate, which reacts with retention of configuration in the presence of an electrophile. Two remarkable features of this transformation are the stereochemical outcome during the formation of the allylzinc species and the complete stereocontrol in the organized six‐membered transition state

  对映体富集的 α-羟基烯丙基硅烷的锌-布鲁克重排产生手性烯丙基锌中间体，在亲电子试剂的存在下与构型保持反应。这种转变的两个显着特征是烯丙基锌物种形成过程中的立体化学结果和有组织的六元过渡态中的完全立体控制，这导致了反应序列中手性的整体和完全转移。
• Preparation of α-silyl- or α,α-bis(silyl)-substituted alkylcopper reagents and their synthetic use
  作者：Junichi Kondo、Atsushi Inoue、Yuki Ito、Hiroshi Shinokubo、Koichiro Oshima

  DOI：10.1016/j.tet.2005.01.101

  日期：2005.3

  Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN center dot 2LiCl afforded 1,1-disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu2CuLi center dot LiCN provided 1-cyano-1-silylalkylcopper species via consecutive double 1,2-migration of alkyl and cyano groups. (c) 2005 Elsevier Ltd. All rights reserved.
• α-Sulfenylation of acylsilanes and aldehydes with N-(phenylthio)succinimide
  作者：Chih-Hao Huang、Kang-Shyang Liao、Surya Kanta De、Yeun-Min Tsai

  DOI：10.1016/s0040-4039(00)00515-3

  日期：2000.5

  The reactions of acylsilanes with N-(phenylthio)succinimide in the presence of p-toluenesulfonic acid in acetonitrile give alpha-sulfenylated acylsilanes in good yields. Aldehydes with alpha-alkyl substituent afford moderate yields of alpha-sulfenylated products under the same conditions. (C) 2000 Elsevier Science Ltd. All rights reserved.
• The Scope and Limitations of Intramolecular Radical Cyclizations of Acylsilanes with Alkyl, Aryl, and Vinyl Radicals
  作者：Sheng-Yueh Chang、Weir-Torn Jiaang、Chaur-Donp Cherng、Kuo-Hsiang Tang、Chih-Hao Huang、Yeun-Min Tsai

  DOI：10.1021/jo9711302

  日期：1997.12.1

  5-Exo cyclizations of primary and secondary radicals with acylsilanes successfully give cyclopentyl silyl ethers. The corresponding 6-exo cyclizations are sensitive to changes of the size of silyl groups. Secondary radicals undergo 6-exo cyclizations with acylsilanes more slowly. Reaction of aryl radical with acylsilane proceeds well for 5-exo cyclization but not for 6-exo cyclization. Vinyl radicals give best results in 5-exo cyclizations with acylsilanes but give low yields (similar to 30%) in 6-exo cyclizations. Intramolecular cyclizations of vinyl radicals with acylsilanes give enol silyl ethers regiospecifically.