tert-butyl-(1-methyl-2-propynyl)diphenylsilane | 247923-45-1

• 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-(1-methyl-2-propynyl)diphenylsilane
• 英文别名: tert-butyl-(1-methyl-prop-2-ynyloxy)diphenylsilane；(but-3-yn-2-yloxy)(tert-butyl)diphenylsilane；1,1a(2)-[(1,1-Dimethylethyl)[(1-methyl-2-propyn-1-yl)oxy]silylene]bis[benzene]；tert-butyl-but-3-yn-2-yloxy-diphenylsilane
• CAS: 247923-45-1
• 化学式: C₂₀H₂₄OSi
• 分子量: 308.495
• InChiKey: XVWMRMBMFLQMJZ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.58
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.3
• 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-(1-methyl-2-propynyl)diphenylsilane 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 0.58h， 生成 1,9-di-(tert-butyldiphenylsilanyloxy)-2,7-decadiyn-5-ol
  参考文献：
  名称：

  Synthesis and Cycloaromatization of a Cyclic Enyne−Allene Prodrug

  摘要：

  A simple and stable cyclic enediynone (4) has been synthesized using an intramolecular Nozaki-Hiyama-Kishi cyclization as the key step. Reaction with a thiolate nucleophile led to rapid cycloaromatization of 4. Trapping experiments using 1,4-cyclohexadiene support the intermediacy of an aromatic diradical in the cycloaromatization.

  DOI：

  10.1021/jo034278w
• 作为产物：
  描述：

  3-丁炔-2-醇 、 叔丁基二苯基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 反应 8.0h， 生成 tert-butyl-(1-methyl-2-propynyl)diphenylsilane
  参考文献：
  名称：

  吲哚-酰胺的金催化分子内串联环化：螺环吡咯烷基二氢吲哚的非对映选择性合成

  摘要：

  吲哚-酰胺的金催化分子内串联环化可一步完成四环螺环吡咯并吲哚啉，并带有一个全碳四元立体中心。然而，当反应在BF的存在下进行3 ⋅Et 2 O，相应的三环螺环基于pyrrolidinoindoline-烯酮通过一个键1,5-氢化移产生。发达的化学方法可在温和条件下的单锅反应中，从吲哚-酰胺类化合物中非对映选择性地直接进入结构多样的多环吡咯烷基二氢吲哚。

  DOI：

  10.1002/asia.201500865

文献信息

• Synthesis of optically enriched 1,2-aminoalcohols by [2,3]-Wittig rearrangements of 3-aza-allylic alcohol derivatives
  作者：Marion Barbazanges、Christophe Meyer、Janine Cossy

  DOI：10.1016/j.tetlet.2008.03.023

  日期：2008.4

  [2,3]-Wittig rearrangements of (E)-3-aza-allylic alcohol derivatives can provide access to syn or anti optically enriched 1,2-aminoalcohols by using a chirality transfer or a chiral auxiliary.

  （E）-3-氮杂-烯丙基醇衍生物的[2，3] -Wittig重排可通过使用手性转移或手性助剂提供合成或反光学富集的1，2-氨基醇的途径。
• Rhodium-Catalyzed Oxygenative [2 + 2] Cycloaddition of Terminal Alkynes and Imines for the Synthesis of β-Lactams
  作者：Insu Kim、Sang Weon Roh、Dong Gil Lee、Chulbom Lee

  DOI：10.1021/ol500856z

  日期：2014.5.2

  which gives β-lactams as products with high trans diastereoselectivity. In the presence of a Rh(I) catalyst and 4-picoline N-oxide, a terminal alkyne is converted to a rhodium ketene species via oxidation of a vinylidene complex and subsequently undergoes a [2 + 2] cycloaddition with an imine to give rise to the 2-azetidinone ring system. Mechanistic studies suggest that the reaction proceeds through

  已经开发了铑催化的末端炔烃和亚胺的氧合[2 + 2]环加成反应，从而得到具有高反式非对映选择性的β-内酰胺。在Rh（I）催化剂和4-picoline N-氧化物的存在下，末端炔烃通过亚乙烯基配合物的氧化转化为铑烯酮物种，随后与亚胺进行[2 + 2]环加成反应，从而生成到2-氮杂环丁酮环系统。机理研究表明，反应是通过金属乙烯酮而不是游离乙烯酮中间体进行的。利用直接从末端炔烃催化生成烯酮物种的新方法为温和条件下Staudinger合成β-内酰胺提供了一种新颖而有效的途径。
• Gold-catalysed cascade rearrangements of ynamide propargyl esters
  作者：Stephen J. Heffernan、James M. Beddoes、Mary F. Mahon、Alan J. Hennessy、David R. Carbery

  DOI：10.1039/c3cc00273j

  日期：——

  The Au(I)-catalysed rearrangement of propargylic esters formed from an ynamide has been studied. The reaction is facile, and when conducted in the presence of a reactive indole nucleophile, leads to a cascade process whereby γ-indolyl α-acyloxyenamides are formed in good yield and excellent E-stereoselectivity.

  已研究了从ynamide生成的丙炔酯的Au(I)催化重排反应。该反应简单易行，在反应活泼的吲哚亲核试剂存在下，会导致级联反应，生成γ-吲哚基α-酰氧烯酮，产率良好且具有优异的E-立体选择性。
• Synthetic studies on the molybdenum cofactor: Total synthesis of pterindithiolenes by direct dithiolene formation from suitable pterin alkynes
  作者：Annada C. Maity、Manas Kumar Das、Sibaprasad Maity、Shyamaprosad Goswami

  DOI：10.1080/00397911.2018.1457697

  日期：2018.7.3

  ABSTRACT A novel, efficient total synthesis of a series of pterindithiolenes (15, 16, 17 and 18) [(5,6-dihydro-[1,4]dithiin or 6,7-dihydro-5H-[1,4]dithiepin systems respectively for six and seven membered dithiolenes] has been reported. The six membered quinoxaline thioketal 9 and seven membered quinoxaline dithiolene 11 have also been synthesized from quinoxaline acetylenic alcohol 5 and the corresponding

  摘要 一系列蝶二硫烯 (15, 16, 17 和 18) [(5,6-dihydro-[1,4] dithiin or 6,7-dihydro-5H-[1,4] dithiepin) 的新型高效全合成分别为六元和七元二硫醇的系统]已经报道。六元喹喔啉硫缩酮 9 和七元喹喔啉二硫醇 11 也分别由喹喔啉炔醇 5 和相应的炔酮 10 合成。五元蝶呤硫缩酮的合成 12还报道了通过与 NBS 反应将 13 和 13 以及 13 转化为二硫烯 14。
• Establishing the concept of aza-[3 + 3] annulations using enones as a key expansion of this unified strategy in alkaloid synthesis
  作者：Aleksey I Gerasyuto、Zhi-Xiong Ma、Grant S Buchanan、Richard P Hsung

  DOI：10.3762/bjoc.9.131

  日期：——

  A successful enone version of an intramolecular aza-[3 + 3] annulation reaction is described here. Use of piperidinium trifluoroacetate salt as the catalyst and toluene as the solvent appears to be critical for a successful annulation. We also demonstrated for the first time that microwave irradiation can accelerate aza-[3 + 3] annulation reactions. An attempt to expand the scope of the enone aza-[3 + 3] annulation was made in the form of propyleine synthesis as a proof of concept. While synthesis of the enone annulation precursor was successfully accomplished, the annulation proved to be challenging and was only modestly successful.

  本文介绍了一种成功的分子内氮杂[3 + 3]环化反应的烯酮版本。使用三氟乙酸哌啶盐作为催化剂和甲苯作为溶剂似乎对于成功的环化反应至关重要。我们还首次证明微波辐射可以加速氮杂[3 + 3]环化反应。为了证明概念，我们尝试扩展烯酮氮杂[3 + 3]环化的范围，以合成丙烯。虽然成功合成了烯酮环化前体，但环化反应仍然具有挑战性，且成功率仅有限。