2-<(tert-Butyldimethylsilyl)oxy>hexanal | 65609-51-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2-<(tert-Butyldimethylsilyl)oxy>hexanal
• 英文别名: 2-(tert-butyldimethylsiloxy)hexanal；α-(tert.-Butyl-dimethylsilyloxy)-capronaldehyd；2-[Tert-butyl(dimethyl)silyl]oxyhexanal
• CAS: 65609-51-0；128950-70-9
• 化学式: C₁₂H₂₆O₂Si
• 分子量: 230.423
• InChiKey: AIYJBBGVDTYEDY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.77
• 重原子数：
  15
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-<(tert-Butyldimethylsilyl)oxy>hexanal 在 吡啶 、 正丁基锂 、 对甲苯磺酸 、 氟化氢吡啶 、 lithium bromide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 正戊烷 为溶剂， 反应 13.5h， 生成 4-(1-bromoethenyl)-5-butyl-2,2-dimethyl-1,3-dioxolane
  参考文献：
  名称：

  1-Bromo-1-lithioethene:  A Practical Reagent in Organic Synthesis

  摘要：

  A reliable preparative scale synthesis of 1-bromo-1-lithioethene is reported. This reagent undergoes clean 1,2-addition with a range of aldehydes and ketones at -110 degrees C to afford the corresponding 2-bromo-1-alken-3-ols in moderate to excellent yield. Trapping with other electrophiles (acylsilanes, chlorosilanes, tributyltin chloride, iodine) cleanly provides practically useful yields of various 1-substituted 1-bromoethene products. Unexpectedly high diastereoselectivities were observed during the addition of 1-bromo-1-lithioethene to alpha-siloxy aldehydes (typically 10:1, Felkin-Ahn control) and protected ketopyranose and ketofuranose sugars (>= 10:1, addition from the less-hindered face). The title organolithium reagent possesses relatively low basicity at low temperature, and is compatible with a variety of common protecting groups. We believe that these unusual properties of 1-bronio-1-lithioethene may originate from the specific crystalline structure of the reagent in which lithium is coordinatively saturated and thus unavailable for chelation.

  DOI：

  10.1021/jo051125v
• 作为产物：
  描述：

  1-庚烯-3-醇 在 咪唑 、 二甲基硫 、 臭氧 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 38.0h， 生成 2-<(tert-Butyldimethylsilyl)oxy>hexanal
  参考文献：
  名称：

  Asymmetric hetero Diels-Alder reaction of .alpha.-alkoxy aldehydes with activated dienes. The scope of Lewis acid chelation-controlled cycloadditions

  摘要：

  DOI：

  10.1021/jo00304a018

文献信息

• Preparation of enol ester epoxides and their ring-opening to α-silyloxyaldehydes
  作者：Gregory K. Friestad、Gopeekrishnan Sreenilayam、Joseph C. Cannistra、Luke M. Slominski

  DOI：10.1016/j.tetlet.2012.06.142

  日期：2012.9

  The Z-selective ruthenium-catalyzed addition of aromatic carboxylic acids to alkynes was followed by dioxirane epoxidation to furnish enol ester epoxides with cis configuration. Upon treatment of enol ester epoxides with tert-butyldimethylsilyl triflate in the presence of 2,6-lutidine, synthetically useful α-silyloxyaldehydes were obtained. This novel transformation was facilitated by microwave irradiation

  Z选择性钌催化的芳香族羧酸向炔烃的加成反应，然后进行二环氧乙烷环氧化，以制备具有顺式构型的烯醇酯环氧化物。在2，6-二甲基吡啶存在下，用三氟甲基叔丁基二甲基甲硅烷基酯处理烯醇酯环氧化物，得到合成上有用的α-甲硅烷氧基醛。微波辐射促进了这种新颖的转化。
• Terminal alkynes from aldehydes via dehydrohalogenation of (Z)-1-iodo-1-alkenes with TBAF
  作者：Mira Beshai、Bhartesh Dhudshia、Ryan Mills、Avinash N. Thadani

  DOI：10.1016/j.tetlet.2008.09.060

  日期：2008.11

  Terminal alkynes were prepared in near quantitative yields via dehydrohalogenation of (Z)-1-iodo-1-alkenes with tetrabutylammonium fluoride (TBAF) under mild conditions. The methodology was expanded to include a one-pot, direct synthesis of terminal alkynes from aldehydes Without the necessity of isolating and purifying the intermediate iodoalkene. (C) 2008 Elsevier Ltd. All rights reserved.
• Ether-directed diastereoselectivity in catalysed Overman rearrangement: comparative studies of metal catalysts
  作者：Ieva Jaunzeme、Aigars Jirgensons

  DOI：10.1016/j.tet.2008.03.099

  日期：2008.6

  Ether-directed diastereoselectivity in Overman rearrangement of delta-methoxy and delta-TBDMSO substituted allylic trichloroacetimidates has been explored using PtCl2, PtCl4, AuCl and AuCl3 catalysts in comparison with commonly used Pd(II) catalysts. For both substrates the use of PtCl2 catalyst gave notably improved anti/syn-ratio of 1,2-aminoalcohol derivatives (anti/syn=11:1 for 5-methoxy; 6:1 for delta-TBDMSO) compared to all metal catalysts known to promote Overman rearrangement. Formation of 2-trichloromethyloxazoline was observed as a dominant side reaction in the metal catalysed rearrangement of a-methoxy substituted allylic trichloroacetimidates considerably reducing the yield of the desired product. This side reaction was suppressed when delta-TBDMS-ether was used as a directing group. (C) 2008 Elsevier Ltd. All rights reserved.
• MIDLAND, M. MARK;KOOPS, ROGER W., J. ORG. CHEM., 55,(1990) N7, C. 5058-5065
  作者：MIDLAND, M. MARK、KOOPS, ROGER W.

  DOI：——

  日期：——