2-but-3-ynyl-[1,3]-dioxane | 251372-57-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: 2-but-3-ynyl-[1,3]-dioxane
• 英文别名: 2-(but-3-ynyl)-1,3-dioxan；2-But-3-ynyl-1,3-dioxane
• CAS: 251372-57-3
• 化学式: C₈H₁₂O₂
• 分子量: 140.182
• InChiKey: YOJHGORETCNEIM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  2-but-3-ynyl-[1,3]-dioxane 在 bis-triphenylphosphine-palladium(II) chloride 、 氢氧化钾 、 copper(l) iodide 、 偶氮二异丁腈 、 三正丁基氢锡 、 二乙胺 作用下， 以 丙酮 为溶剂， 反应 20.0h， 生成 toluene-4-silfonic acid 7-[1,3]dioxan-2-ylhept-4-en-2-ynyl ester
  参考文献：
  名称：

  Stereocontrolled Synthesis of Functionalized Bicyclic α-Methylene Butyrolactones via Tungsten-Mediated Intramolecular Allylation of Aldehydes

  摘要：

  The syntheses of a series of CpW(CO)(2)(pi-gamma-lactonyl) complexes bearing a tethered aldehyde are described. These pi-allyl complexes are prepared as either syn- or anti-stereoisomers. Treatment of these dicarbonyl complexes with NOBF4 and NaI in CH3CN effects an intramolecular allylation of the tethered aldehyde, yielding bicyclic alpha-methylene butyrolactones comprising a homoallylic alcohol. Both syn- and anti-isomers of tungsten-pi-allyl compounds produce the same alpha-methylene butyrolactones. The cyclizations proceed with high diastereoselectivities to give only the cis-fused bicyclic gamma-lactones. The preference for cis-fused stereoselection can be rationalized based on a tricyclic transition state mechanism.

  DOI：

  10.1021/jo9909002
• 作为产物：
  描述：

  2-(2-溴乙基)-1,3-二恶烷 、 乙炔锂乙二胺配合物 在 六甲基磷酰三胺 、 四甲基乙二胺 作用下， 以 四氢呋喃 为溶剂， 以73%的产率得到2-but-3-ynyl-[1,3]-dioxane
  参考文献：
  名称：

  全合成顺式喜树碱。

  摘要：

  描述了（+）-顺式-sylvaticin的不对称全合成。关键步骤包括使用高锰酸盐介导的1,5-二烯的氧化环化反应合成两个主要片段2和3，以及使用催化有效的束缚RCM结合这些含THF的片段。另外，发现t-BuP 4碱能可靠地促进丁烯内酯前体片段4的快速烷基化。

  DOI：

  10.1021/ol800767e

文献信息

• Rh(<scp>iii</scp>)-Catalyzed olefination to build diverse oxazole derivatives from functional alkynes
  作者：Yuan He、Ting Zheng、Yin-Hui Huang、Lin Dong

  DOI：10.1039/d1ob00507c

  日期：——

  A novel Rh(III)-catalyzed olefination reaction of oxazoles to generate diverse oxazole skeleton derivatives has been realized by directly using oxazole as the directing group. The reaction could tolerate many functional groups, affording complex oxazole derivatives with long chain alkenyls in moderate to good yields, which might find applications in the construction of diverse compounds.

  通过直接使用恶唑作为导向基团，实现了一种新颖的Rh( III )催化恶唑烯化反应生成多种恶唑骨架衍生物。该反应可以耐受许多官能团，以中等至良好的产率提供具有长链烯基的复杂恶唑衍生物，这可能在构建多种化合物中得到应用。
• Asymmetric Synthesis of β-Lactams through Copper-Catalyzed Alkyne-Nitrone Coupling with a Prolinol-Phosphine Chiral Ligand
  作者：Yurie Takayama、Takaoki Ishii、Hirohisa Ohmiya、Tomohiro Iwai、Martin C. Schwarzer、Seiji Mori、Tohru Taniguchi、Kenji Monde、Masaya Sawamura

  DOI：10.1002/chem.201702070

  日期：2017.6.22

  Prolinol–phosphine chiral ligands enabled highly enantioselective copper‐catalyzed intermolecular alkyne–nitrone coupling (Kinugasa reaction) to produce 1,3,4‐trisubstituted chiral β‐lactams. A high level of enantiocontrol was achieved not only with aryl‐ or alkenylacetylenes but also with alkylacetylenes, which were important but unfavorable substrates in the previously reported protocols. Two‐point

  脯氨醇-膦的手性配体使得高度对映选择性的铜催化的分子间炔-硝基偶联（Kinugasa反应）产生了1,3,4-三取代的手性β-内酰胺。不仅使用芳基或烯基乙炔，而且使用烷基乙炔都可以实现高水平的对映体控制，这在先前报道的方案中是重要的但不利的底物。提出了由OH-H···O和C（sp 3）-H··· O的氢键构成的手性配体与氮氧阴离子的两点氢键。
• Stereocontrolled Synthesis of Functionalized Bicyclic α-Methylene Butyrolactones via Tungsten-Mediated Intramolecular Allylation of Aldehydes
  作者：Lin-Hun Shiu、Yang-Lian Li、Chien-Le Li、Ching-Yu Lao、Chen、Chin-Hui Yu、Rai-Shung Liu

  DOI：10.1021/jo9909002

  日期：1999.10.1

  The syntheses of a series of CpW(CO)(2)(pi-gamma-lactonyl) complexes bearing a tethered aldehyde are described. These pi-allyl complexes are prepared as either syn- or anti-stereoisomers. Treatment of these dicarbonyl complexes with NOBF4 and NaI in CH3CN effects an intramolecular allylation of the tethered aldehyde, yielding bicyclic alpha-methylene butyrolactones comprising a homoallylic alcohol. Both syn- and anti-isomers of tungsten-pi-allyl compounds produce the same alpha-methylene butyrolactones. The cyclizations proceed with high diastereoselectivities to give only the cis-fused bicyclic gamma-lactones. The preference for cis-fused stereoselection can be rationalized based on a tricyclic transition state mechanism.
• Total Synthesis of <i>cis</i>-Sylvaticin
  作者：Lynda J. Brown、Ian B. Spurr、Stephen C. Kemp、Nicholas P. Camp、Karl R. Gibson、Richard C. D. Brown

  DOI：10.1021/ol800767e

  日期：2008.6.1

  An asymmetric total synthesis of (+)-cis-sylvaticin is described. Key steps include the use of permanganate-mediated oxidative cyclization of 1,5-dienes to synthesize the two major fragments 2 and 3 and a catalytically efficient tethered RCM to unite these THF-containing fragments. In addition, t-BuP 4 base was found to reliably promote rapid alkylation of the butenolide precursor fragment 4.

  描述了（+）-顺式-sylvaticin的不对称全合成。关键步骤包括使用高锰酸盐介导的1,5-二烯的氧化环化反应合成两个主要片段2和3，以及使用催化有效的束缚RCM结合这些含THF的片段。另外，发现t-BuP 4碱能可靠地促进丁烯内酯前体片段4的快速烷基化。