1-(triisopropylsilyl)non-1-yn-3-one | 357429-54-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-(triisopropylsilyl)non-1-yn-3-one
• 英文别名: 1-tri(propan-2-yl)silylnon-1-yn-3-one
• CAS: 357429-54-0
• 化学式: C₁₈H₃₄OSi
• 分子量: 294.553
• InChiKey: ZGFAXXGLNFKZEJ-UHFFFAOYSA-N

物化性质

• 沸点：
  342.4±11.0 °C(Predicted)
• 密度：
  0.858±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5.75
• 重原子数：
  20.0
• 可旋转键数：
  8.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为反应物：
  描述：

  1-(triisopropylsilyl)non-1-yn-3-one 在 chloro([(S,2S)-(−)-2-amino-1,2-diphenylethyl](4-toluenesulfonyl)amido)(mesitylene)ruthenium (II) 作用下， 以 异丙醇 为溶剂， 以96 %的产率得到
  参考文献：
  名称：

  前列腺素 F2α 的一般催化剂控制途径

  摘要：

  我们报告了前列腺素 F2 α及其类似物的一般催化剂控制途径。该方法在外消旋双环烯丙基氯和带有手性醇的烯基硼酸酯之间使用 Rh 催化的动力学不对称铃木 - 宫浦偶联反应，得到带有 3 个连续立构中心的环戊基中间体。在所有检查的情况下，该路线提供 99% ee 的高级中间体作为单一非对映异构体，环戊烷核心的绝对立体化学由配体控制。合成了可用于生产前列腺素类似物（如比马前列素、拉坦前列素、氟前列醇和氯前列醇）的中间体。最后两个立体中心是通过 Pd 催化的 Tsuji-Trost 烷基化和碘内酯化安装的。PG F2的合成在 16 个最长的线性步骤中以 19% 的收率实现了α 。

  DOI：

  10.1021/acs.orglett.2c03718
• 作为产物：
  描述：

  庚酸 在 4-二甲氨基吡啶 、 正丁基锂 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 、 三乙胺 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.75h， 生成 1-(triisopropylsilyl)non-1-yn-3-one
  参考文献：
  名称：

  前列腺素 F2α 的一般催化剂控制途径

  摘要：

  我们报告了前列腺素 F2 α及其类似物的一般催化剂控制途径。该方法在外消旋双环烯丙基氯和带有手性醇的烯基硼酸酯之间使用 Rh 催化的动力学不对称铃木 - 宫浦偶联反应，得到带有 3 个连续立构中心的环戊基中间体。在所有检查的情况下，该路线提供 99% ee 的高级中间体作为单一非对映异构体，环戊烷核心的绝对立体化学由配体控制。合成了可用于生产前列腺素类似物（如比马前列素、拉坦前列素、氟前列醇和氯前列醇）的中间体。最后两个立体中心是通过 Pd 催化的 Tsuji-Trost 烷基化和碘内酯化安装的。PG F2的合成在 16 个最长的线性步骤中以 19% 的收率实现了α 。

  DOI：

  10.1021/acs.orglett.2c03718

文献信息

• Radical-Induced Metal-Free Alkynylation of Aldehydes by Direct CH Activation
  作者：Xuesong Liu、Linqian Yu、Mupeng Luo、Jidong Zhu、Wanguo Wei

  DOI：10.1002/chem.201501094

  日期：2015.6.8

  A direct C(sp2)H alkynylation of aldehyde C(O)H bonds with hypervalent iodine alkynylation reagents provides ynones under metal‐free conditions. In this method, 1‐[(triisopropylsilyl)ethynyl]‐1,2‐benziodoxol‐3(1H)‐one (TIPS‐EBX) constitutes an efficient alkynylation reagent for the introduction of the triple bond. The substrate scope is extended to a variety of (hetero)aromatic, aliphatic, and α

  直接C（SP 2） ħ炔基的醛C（O） H带高价碘炔基试剂键提供不含金属的条件下ynones。在这种方法中，1-[（（三异丙基甲硅烷基）乙炔基] -1，2-苯并恶唑醇-3（1 H）-one（TIPS-EBX）构成引入三键的有效炔基化试剂。底物的范围扩展到各种（杂）芳族，脂族和α，β-不饱和醛。
• Metal-free carbonyl C(sp²)–H oxidative alkynylation of aldehydes using hypervalent iodine reagents leading to ynones
  作者：Xuan-Hui Ouyang、Ren-Jie Song、Cheng-Yong Wang、Yuan Yang、Jin-Heng Li

  DOI：10.1039/c5cc03362d

  日期：——

  The metal-free and facile synthesis of ynonesviacarbonyl C(sp²)–H oxidative alkynylation of aldehydes with enynyl benziodoxolones is presented.

  通过使用烯基苯碘酚醇与醛类化合物进行羰基C(sp2)-H氧化炔基化反应，实现了无金属和简便的合成炔酮。
• 1,3-Diethynylallenes: Carbon-Rich Modules for Three-Dimensional Acetylenic Scaffolding
  作者：Robert Livingston、Liam R. Cox、Severin Odermatt、François Diederich

  DOI：10.1002/1522-2675(200210)85:10<3052::aid-hlca3052>3.0.co;2-4

  日期：2002.10

  Regioselective Pd-0-catalyzed cross-coupling of substrates, which bear bispropargylic leaving groups with silyl-protected alkynes, has provided access to a variety of 1.3-diethynylailenes, a new family of modules for three-dimensional acetylenic scaffolding. In enantiomerically pure form, these C-rich building blocks could provide access - by oxidative oligomerization - to a fascinating new class of helical oligomers and polymers with all-carbon backbones (Fig. 2). In the first of two routes. a bispropargylic epoxide underwent ring opening during S(N)2'-type cross-coupling. and the resulting alkoxide was silyl-protected, providing 1,3-diethynylailenes (+/-)-8, (+/-)-12 (Scheme 3), and (+/-)-15 (Scheme 5). A more general approach involved bispropargylic carbonates or esters as substrates (Scheme 6-8), and this route was applied to the preparation of a series of 13-diethyrrylallenes to investigate how their overall stability against undesirable [2 + 2] cycloaddition is affected by the nature of the substituents at the allene moiety. The investigation showed that the 1,3-diethynylallene chromophore is stable against [2 + 2] cycloaddition only when protected by steric bulk and when additional relectron delocalization is avoided. The regioselectivity of the cross-coupling to the bispropargylic substrates is entirely controlled by steric factors: attack occurs at the alkyne moiety bearing the smaller substituent (Schemes 9 and 10). Oxidative Hay coupling of the terminally mono-deprotected 1.3-diethynylallene (+/-)-49 afforded the first dimer 50, probably as a mixture of two diastereoisomers (Scheme 12). Attempts to prepare a silyl-protected tetraethynylallene by the new methodology failed (Scheme 13). Control experiments (Schemes 14 - 16) showed that the Pd-0-catalyzed cross-coupling to butadiyne moieties in the synthesis of this still-elusive chromophore requires forcing conditions under which rapid [2 + 2] cycloaddition of the initial product cannot be avoided.
• A General Synthesis of Ynones from Aldehydes via Oxidative C–C bond Cleavage under Aerobic Conditions
  作者：Zhaofeng Wang、Li Li、Yong Huang

  DOI：10.1021/ja506352b

  日期：2014.9.3

  We describe a direct synthesis of various ynones from readily available aldehydes and hypervalent alkynyl iodides. In this method, a gold catalyst and a secondary amine work synergistically to produce the trisubstituted allenyl aldehyde, which can be converted to the desired ynone through an in situ C-C bond oxidative cleavage using molecular oxygen.
• 1,3-Diethynylallenes: New Modules for Three-Dimensional Acetylenic Scaffolding
  作者：Robert C. Livingston、Liam R. Cox、Volker Gramlich、François Diederich

  DOI：10.1002/1521-3773(20010618)40:12<2334::aid-anie2334>3.0.co;2-7

  日期：2001.6.18

  Regioselective Pd0 -catalyzed cross-coupling of bispropargylic precursors 1 with silyl-protected alkynes gave rise to the first 1,3-diethynylallenes 2 [Eq. (1), LG=leaving group]. In enantiomerically pure form, these novel carbon-rich modules could provide access-by oxidative oligomerization-to a fascinating new class of helical oligomers and polymers.