triisopropyl((trimethylsilyl)buta-1,3-diyn-1-yl)silane | 920282-74-2

• 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: triisopropyl((trimethylsilyl)buta-1,3-diyn-1-yl)silane
• 英文别名: Trimethyl{4-[tri(propan-2-yl)silyl]buta-1,3-diyn-1-yl}silane；trimethyl-[4-tri(propan-2-yl)silylbuta-1,3-diynyl]silane
• CAS: 920282-74-2
• 化学式: C₁₆H₃₀Si₂
• 分子量: 278.585
• InChiKey: SOZUPDUHNXOZIO-UHFFFAOYSA-N

物化性质

• 沸点：
  298.4±23.0 °C(Predicted)
• 密度：
  0.839±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.09
• 重原子数：
  18
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 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：

  triisopropyl((trimethylsilyl)buta-1,3-diyn-1-yl)silane 在 1,1'-双(二苯膦基)二茂铁二氯化钯(II)二氯甲烷复合物 、 methyllithium lithium bromide 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 (4-Tritylphenyl) 10-tri(propan-2-yl)silyldeca-5,7,9-triynoate
  参考文献：
  名称：

  寡炔两亲物及其轮烷的简便合成

  摘要：

  含有一系列共轭三键（寡炔）的富含碳的有机化合物是相关的合成目标，但需要改进获得带有官能团的寡炔的途径。在这里，我们报告了两种具有糖苷或羧酸极性头基的寡炔两亲物的直接合成，研究了它们在水性介质中的自组装行为，以及它们作为前体用于形成具有环糊精主体的寡炔轮烷的前体。为此，我们使用了单、二或三乙炔结构单元，可以在原位获得相应的乙炔锌，并通过几个合成步骤有效地延长低聚炔链段。Negishi 耦合协议。此外，我们表明获得的寡炔衍生物可以脱保护以产生相应的两亲物。根据它们的头部基团，这些两亲物的超分子自组装在水性介质中产生了不同类型的富碳胶体聚集体。此外，它们的两亲性被用于在水中使用简单的主客体化学制备新型低聚环糊精轮烷。

  DOI：

  10.1039/c4sc03154g
• 作为产物：
  描述：

  二(三甲基甲硅烷基)乙炔 在 aluminum (III) chloride 、 正丁基锂 、 四溴化碳 、 三苯基膦 作用下， 以 正己烷 、 二氯甲烷 为溶剂， 生成 triisopropyl((trimethylsilyl)buta-1,3-diyn-1-yl)silane
  参考文献：
  名称：

  Chiral Propargyl Alcohols via the Enantioselective Addition of Terminal Di- and Triynes to Aldehydes

  摘要：

  The enantioselective addition of di- and triynes to aldehydes is presented, including the first examples of an asymmetric triyne addition. Modification of the Carreira alkynylation protocol shows that addition of diynes and triynes to alpha-branched aldehydes can be complete in as little as 4 h, and these reactions give good yields and enantioselectivities (up to 98% ee) for di- and triynes tested (aryl, alkyl, and silyl). It is shown for two cases (20 and 24) that products of this asymmetric addition reaction can undergo further manipulation (desilylation and triazole formation) without affecting the enantiopurity.

  DOI：

  10.1021/jo2008719

文献信息

• Gold-Catalyzed Cadiot-Chodkiewicz-type Cross-Coupling of Terminal Alkynes with Alkynyl Hypervalent Iodine Reagents: Highly Selective Synthesis of Unsymmetrical 1,3-Diynes
  作者：Xiangdong Li、Xin Xie、Ning Sun、Yuanhong Liu

  DOI：10.1002/anie.201702833

  日期：2017.6.6

  A new and efficient method for the synthesis of unsymmetrical 1,3‐butadiynes by gold‐catalyzed C(sp)–C(sp) cross‐coupling of terminal alkynes with alkynyl hypervalent iodine(III) reagents has been developed. The reaction features high selectivity and efficiency, mild reaction conditions, wide substrate scope, and functional‐group compatibility, and is a highly attractive complement to existing methods

  开发了一种新的高效方法，该方法通过末端炔烃与炔基高价碘（III）试剂的金催化C（sp）–C（sp）交叉偶联来合成不对称1,3-丁二炔。该反应具有高选择性和高效率，温和的反应条件，广泛的底物范围和官能团相容性，是对现有方法的极具吸引力的补充。机理研究表明，形成菲咯啉基连接的金（I）络合物对于目标转化的效率和选择性至关重要。
• Synthesis of Long, Palladium End-Capped Polyynes through the Use of Asymmetric 1-Iodopolyynes
  作者：Bartłomiej Pigulski、Nurbey Gulia、Sławomir Szafert

  DOI：10.1002/chem.201502737

  日期：2015.12.1

  The synthesis of a unique series of long, asymmetric 1‐iodopolyynes (1‐CnI and 2‐CnI) with the sp‐hybridized carbon chain up to a decapentayne is reported. These compounds were then used as substrates in reactions with Pd(PPh3)4 leading to another series of palladium end‐capped polyynes, which were unstable in solution. Organometallic octatetraynes 1‐C8[Pd]I, 2‐C8[Pd]I, and decapentayne 1‐C10[Pd]I

  的一系列独特的长，非对称1- iodopolyynes（合成1 -C Ñ I和2 -C Ñ报道与SP-杂交碳链长达decapenTAyne I）。然后将这些化合物用作与Pd（PPh 3）4反应的底物，生成另一系列的钯封端的聚炔，它们在溶液中不稳定。有机金属辛酸1– C 8 [Pd] I，2– C 8 [Pd] I和十碳炔1– C 10[Pd] I是迄今为止报道的碳链最长的钯封端的聚炔化合物。通过NMR，HRMS（ESI），IR，TGA-DTA和UV / Vis技术对所有配合物及其有机前体进行了充分表征，两种甲硅烷基保护的前体和一种钯配合物的X射线晶体结构为呈现。钯物种的合成方法被设想为合成不稳定的有机金属多炔的通用途径。
• Late-stage diversification strategy for synthesizing ynamides through copper-catalyzed diynylation and azide–alkyne cycloaddition
  作者：Ryohei Kawakami、Suguru Usui、Norihiro Tada、Akichika Itoh

  DOI：10.1039/d2cc05575a

  日期：——

  diversification strategy for synthesizing ynamides has been developed. This strategy was enabled by the copper-catalyzed direct electrophilic diynylation of sulfonamides with a novel triisopropylsilyl diynyl benziodoxolone, deprotection, and the late-stage chemoselective copper-catalyzed azide–alkyne cycloaddition sequence, which yields various complex molecule-derived ynamides with pyrene, amino acid, nucleoside

  已开发出用于合成 ynamides 的后期多样化策略。该策略是通过铜催化的磺胺类化合物与新型三异丙基甲硅烷基二炔基苯并多索酮的直接亲电二炔基化、脱保护和后期化学选择性铜催化的叠氮-炔烃环加成序列实现的，从而产生各种复杂的分子衍生的炔胺与芘、氨基酸、核苷和N-乙酰葡糖胺作为取代基。
• Regioselective Trapping of Terminal Di-, Tri-, and Tetraynes with Benzyl Azide
  作者：Thanh Luu、Robert McDonald、Rik R. Tykwinski

  DOI：10.1021/ol062522a

  日期：2006.12.1

  The reaction of benzyl azide with terminal di-, tri-, and tetraynes appended with a range of functional groups has been explored. Standard reaction conditions for BnN3 catalyzed by CuSO(4)(.)5H(2)O gave alkynyl, butadiynyl, and hexatriynyl triazoles in moderate to good yields. The reaction proceeds regioselectively as determined by the X-ray crystallographic analysis of three derivatives (1c, 1d, and 3c), and no evidence of multiple azide addition to the polyyne framework is observed.
• Syntheses of (+)-Complanadine A and Lycodine Derivatives by Regioselective [2 + 2 + 2] Cycloadditions
  作者：Changxia Yuan、Chih-Tsung Chang、Dionicio Siegel

  DOI：10.1021/jo400695c

  日期：2013.6.7

  The dimeric alkaloid complanadine A has shown promise in regenerative science, promoting neuronal growth by inducing the secretion of growth factors from glial cells. Through the use of tandem, cobalt-mediated [2 + 2 + 2] cycloaddition reactions, two synthetic routes have been developed with different sequences for the formation of the unsymmetric bipyridyl core. The regioselective formation of each of the pyridines was achieved based on the inherent selectivity of the molecules or by reversing the regioselectivity through the addition of Lewis bases. This strategy has been successfully employed to provide laboratory access to complanadine A as well as structurally related compounds possessing the lycocline core.