2-isopropyl-1-(triisopropylsiloxy)ethyne | 122760-68-3

• 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: 2-isopropyl-1-(triisopropylsiloxy)ethyne
• 英文别名: 3-methyl-1-(triisopropylsiloxy)-1-butyne；Silane, [(3-methyl-1-butynyl)oxy]tris(1-methylethyl)-；3-methylbut-1-ynoxy-tri(propan-2-yl)silane
• CAS: 122760-68-3
• 化学式: C₁₄H₂₈OSi
• 分子量: 240.461
• InChiKey: CYPGIANBWRLFAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 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：

  2-isopropyl-1-(triisopropylsiloxy)ethyne 在 盐酸 、 正丁基锂 、 甲基锂 作用下， 以 甲醇 为溶剂， 反应 40.0h， 生成 2,2,5-trimethyl-9-isopropyl-2,5,6,7-tetrahydro-8-(triisopropylsiloxy)phenaleno<1,9-bc>furan
  参考文献：
  名称：

  Total Synthesis of the Phenalenone Diterpene Salvilenone

  摘要：

  The application of a photochemical aromatic annulation strategy in a highly efficient total synthesis of the phenalenone diterpene salvilenone is reported. The pivotal step in the synthesis involves the assembly of the key dihydrophenalene 29 in one step via an annulation involving the siloxyalkyne 28 and either diazo ketone 8 or 9. The synthesis of the alpha-benzosuberone 8 was achieved in three steps beginning with 2-methylcyclopentanone by a route featuring an ''aryne-enolate condensation'' reaction. The alternative aromatic annulation substrate, the beta-benzosuberone 9, was prepared in four steps by a route based on the regiocontrolled ring expansion of the alpha-methylenetetralin 27. The key aromatic annulation was then accomplished by irradiating a mixture of either diazo ketone 8 or 9 and 1.4 equiv of the siloxyalkyne 28 in 1,2-dichloroethane at 20-25 degrees C using a standard Rayonet photochemical reactor. The reaction mixture was next diluted with an equal volume of solvent and heated overnight at 80 degrees C to complete the annulation; concentration and chromatographic purification furnished the tricyclic phenol 29 as colorless crystals in 60-71% yield. Finally, annulation of the furan ring and oxidation required three steps and provided the phenalenone diterpene in good yield. The synthetic routes described herein provide access to salvilenone in only seven or eight steps (via the alpha- and beta-benzosuberone strategies, respectively), half the number of steps required using the classical linear substitution approach reported previously. These highly efficient syntheses demonstrate the ability of the photochemical aromatic annulation strategy to dramatically streamline the synthesis of polycyclic aromatic compounds.

  DOI：

  10.1021/ja00100a009
• 作为产物：
  描述：

  三异丙基氯硅烷 、 异丁酸乙酯 、 二溴甲烷 在 正丁基锂 、 2,2,6,6-tetramethylpiperidinyl-lithium 作用下， 生成 2-isopropyl-1-(triisopropylsiloxy)ethyne
  参考文献：
  名称：

  Trialkylsilyloxyalkynes: Synthesis and aromatic annulation reactions

  摘要：

  DOI：

  10.1016/s0040-4039(00)80640-1

文献信息

• A benzannulation strategy for the synthesis of phenols and heteroaromatic compounds based on the reaction of (trialkylsilyl)vinylketenes with lithium ynolates
  作者：Wesley F. Austin、Yongjun Zhang、Rick L. Danheiser

  DOI：10.1016/j.tet.2007.10.113

  日期：2008.1

  (Trialkylsilyl)vinylketenes react with lithium ynolates to generate 3-(oxido)dienylketenes, which undergo rapid 6π-electrocyclization. The ultimate products of this benzannulation are highly substituted resorcinol monosilyl ethers, which are formed via a [1,3] carbon to oxygen silyl group shift. Further transformations of the benzannulation products are described providing efficient access to ortho-benzoquinones

  （三烷基甲硅烷基）乙烯基烯酮与炔醇锂反应生成 3-（氧化）二烯基烯酮，其经历快速 6π-电环化。这种苯环化的最终产物是高度取代的间苯二酚单甲硅烷基醚，它是通过 [1,3] 碳到氧甲硅烷基的转变形成的。描述了苯并环化产物的进一步转化，提供了对邻苯醌和苯并呋喃、苯并氧杂和苯并氧辛环系统的有效访问。
• An annulation method for the synthesis of highly substituted polycyclic aromatic and heteroaromatic compounds
  作者：Rick L. Danheiser、Ronald G. Brisbois、James J. Kowalczyk、Raymond F. Miller

  DOI：10.1021/ja00164a033

  日期：1990.4

  A general strategy for the synthesis of highly substituted polycyclic aromatic and heteroaromatic compounds has been developed. The new aromatic annulation is achieved simply by the irradiation of a dichloroethane solution of an acetylene derivative and a vinyl or aryl α-diazo ketone. Mechanistically, the reaction proceeds via the photochemical Wolff rearrangement of the diazo ketone to generate an

  已经开发了合成高度取代的多环芳族和杂芳族化合物的一般策略。通过辐照乙炔衍生物和乙烯基或芳基α-重氮酮的二氯乙烷溶液，可以简单地实现新的芳香环化。从机制上讲，该反应通过重氮酮的光化学沃尔夫重排进行，生成芳基或乙烯基烯酮，然后是三个周环反应的级联反应。用该方法可制备多种取代酚类、萘类、苯并呋喃类、苯并噻吩类、吲哚类、咔唑类
• Total synthesis of dan shen diterpenoid quinones
  作者：Rick L. Danheiser、David S. Casebier、Jennifer L. Loebach

  DOI：10.1016/s0040-4039(00)91882-3

  日期：1992.2

  A photochemical aromatic annulation strategy provides efficient synthetic routes to the diterpenoid quinones (+)-danshexinkun A, danshexinkun B, danshexinkun C, (-)-dihydrotanshinone I, and tanshinone I.
• Reactions of (Trialkylsilyl)vinylketenes with Lithium Ynolates:  A New Benzannulation Strategy
  作者：Wesley F. Austin、Yongjun Zhang、Rick L. Danheiser

  DOI：10.1021/ol051307b

  日期：2005.9.1

  (Trialkylsilyl)vinylketenes react with lithium ynolates to produce highly substituted phenols in a new benzannulation strategy that proceeds via the 6 pi electrocyclization of an intermediate 3-(oxido)dienylketene.
• Aromatic Annulation Strategy for the Synthesis of Angularly-Fused Diterpenoid Quinones. Total Synthesis of (+)-Neocryptotanshinone, (-)-Cryptotanshinone, Tanshinone IIA, and (.+-.)-Royleanone
  作者：Rick L. Danheiser、David S. Casebier、Fariborz Firooznia

  DOI：10.1021/jo00131a006

  日期：1995.12

  The application of a photochemical aromatic annulation strategy in highly efficient total syntheses of several diterpenoid quinones isolated from the traditional Chinese medicine Dan Shen is reported. The pivotal step in each synthesis involves the assembly of a key tricyclic intermediate via the application of a recently developed ''second-generation'' photochemical aromatic annulation method for the construction of highly substituted aromatic systems. In the total synthesis of neocrypto-tanshinone,;the synthesis of the requisite diazo ketone annulation substrate 7 was achieved using palladium-mediated coupling reactions and an intramolecular Friedel-Crafts cyclization to form key carbon-carbon bonds. The pivotal aromatic annulation reaction was then accomplished by irradiating a solution of the diazo ketone 7 and the readily available siloxyalkyne 6 in benzene at room temperature. The desired tricyclic phenol 16 was produced in 58-65% yield and was then converted to (+)-neocryptotanshinone (1) by treatment with tetra-n-butylammonium fluoride in the presence of oxygen. Cyclization to generate (-)-cryptotanshinone (2) was accomplished in high yield by brief exposure of 1 to an ethanolic solution of concentrated sulfuric acid, and dehydrogenation of 2 with DDQ furnished tanshinone IIA (3). As a further demonstration of the utility of the photochemical aromatic annulation strategy in the construction of angularly-fused diterpenes, the total synthesis of(+/-)-royleanone (4) was also investigated. Irradiation of a solution of the diazo ketone 18 and siloxyalkyne 25 produced the tricyclic intermediate 26, which was converted in two steps to royleanone by desilylation and oxidation.