(4-{tert-butyl(dimethyl)silyl}oxy-butyl)(triphenyl)phosphonium iodide

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (4-{tert-butyl(dimethyl)silyl}oxy-butyl)(triphenyl)phosphonium iodide
• 英文别名: 4-[Tert-butyl(dimethyl)silyl]oxybutyl-triphenylphosphanium;iodide
• 化学式: C₂₈H₃₈OPSi*I
• 分子量: 576.573
• InChiKey: FMFFCTYJACBOPQ-UHFFFAOYSA-M

计算性质

• 辛醇/水分配系数(LogP)：
  3.79
• 重原子数：
  32
• 可旋转键数：
  10
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (4-{tert-butyl(dimethyl)silyl}oxy-butyl)(triphenyl)phosphonium iodide 在 sodium hydroxide 、 水 作用下， 以 乙醇 为溶剂， 反应 1.0h， 以80%的产率得到tert-Butyl-[4-(diphenyl-phosphinoyl)-butoxy]-dimethyl-silane
  参考文献：
  名称：

  Total Synthesis of Brevetoxin A: Part 4: Final Stages and Completion

  摘要：

  The total synthesis of brevetoxin A is described, Our methodology of palladium-catalyzed couplings with cyclic ketene acetal phosphates was utilized to functionalize nine-membered ring lactone 4 followed by a [4+2] singlet oxygen addition to the resulting 1,3-diene (6), The product endoperoxide (7) was transformed into coupling partners 3a and 3b to be reacted with aldehyde 2, Our first attempted union of 3a and aldehyde 2 failed, most probably due to steric hindrance, which led us to explore other olefination coupling reactions. Horner- Wittig type coupling was found to be successful on advanced model systems: diphenylphosphine oxides 21 and 28 were each coupled with aldehyde 2. Key intermediates 3b and 2 were successfully coupled and ring F oxocene (44) was cyclized through the hydroxy dithioketal cyclization methodology, The final manipulations were then executed to complete the first total synthesis of brevetoxin A.

  DOI：

  10.1002/(sici)1521-3765(19990201)5:2<646::aid-chem646>3.0.co;2-e
• 作为产物：
  描述：

  叔丁基二甲基氯硅烷 在 sodium iodide 作用下， 以 乙腈 为溶剂， 生成 (4-{tert-butyl(dimethyl)silyl}oxy-butyl)(triphenyl)phosphonium iodide
  参考文献：
  名称：

  光氧化铬催化剂促进自由基阳离子环加成反应

  摘要：

  描述了所选Cr III配合物促进自由基阳离子环加成的光氧化能力。这些络合物具有足够长的激发态，可以氧化富电子的烯烃，从而引发[4 + 2]过程。这些金属种类增加了在光氧化还原系统中探索的催化剂的范围，因为它们具有独特的性质，可导致与较常用的钌或铱催化剂产生不同的反应性。

  DOI：

  10.1002/anie.201501220

文献信息

• Radical Cation Diels–Alder Reactions by TiO₂ Photocatalysis
  作者：Kaii Nakayama、Naoya Maeta、Genki Horiguchi、Hidehiro Kamiya、Yohei Okada

  DOI：10.1021/acs.orglett.9b00526

  日期：2019.4.5

  Radical cation Diels–Alder reactions by titanium dioxide (TiO2) photocatalysis in lithium perchlorate/nitromethane solution are described. TiO2 photocatalysis promotes reactions between electron-rich dienes and dienophiles, which would otherwise be difficult to accomplish due to electronic mismatching. The reactions are triggered by hole oxidation of the dienophile and are completed by the excited

  描述了在高氯酸锂/硝基甲烷溶液中通过二氧化钛（TiO 2）光催化的自由基阳离子Diels–Alder反应。TiO 2光催化促进富电子二烯与亲二烯体之间的反应，否则由于电子失配而难以完成。该反应由亲二烯体的空穴氧化触发，并且通过在没有任何牺牲底物的情况下在分散的表面上自由基阳离子中间体的激发电子还原来完成。
• Catalytic Oxygenative Allylic Transposition of Alkenes into Enones with an Azaadamantane‐Type Oxoammonium Salt Catalyst
  作者：Shota Nagasawa、Yusuke Sasano、Yoshiharu Iwabuchi

  DOI：10.1002/chem.201702512

  日期：2017.8

  The first catalytic oxygenative allylic transposition of unactivated alkenes into enones has been developed using an oxoammonium salt as the catalyst. This reaction converts various tri- and trans-disubstituted alkenes into their corresponding enones with transposition of their double bonds at ambient temperature in good yields. The use of a less-hindered azaadamantane-type oxoammonium salt as the catalyst

  使用氧代铵盐作为催化剂，已开发出未活化的烯烃向烯酮的第一个催化氧化烯丙基转移。该反应将各种三和反双取代的烯烃转化成其相应的烯酮，并在环境温度下以双键的换位以良好的收率。使用较少受阻的氮杂金刚烷型氧铵盐作为催化剂，并使用两种不同的化学计量氧化剂（即碘代苯二乙酸盐和单过氧邻苯二甲酸镁六水合物（MMPP·6 H 2 O））的组合，对于有效促进烯酮的形成至关重要。
• A tandem radical macrocyclisation-transannular cyclisation approach towards the taxanes
  作者：Stephen A. Hitchcock、Stephen J. Houldsworth、Gerald Pattenden、David C. Pryde、Nicholas M. Thomson、Alexander J. Blake

  DOI：10.1039/a805268i

  日期：——

  Separate treatment of the iodotrienedione 19 and the iododienynedione 38 with Bu3SnH–AIBN produces the corresponding taxane ring systems 25 (25–30%) and 56 (50–60%) respectively by way of tandem radical macrocyclisation-radical transannular cyclisations. By contrast the analogous iodopolyenones 61, 63, 65a, 66a, 86a and 87a, together with the corresponding iodoenynones 39a and 59 failed to undergo similar tandem radical reactions, and instead gave products resulting from direct reduction of the carbon–iodine bonds in these substrates. The structures of the taxane analogues 25 and 56 followed from analysis of their NMR spectroscopic data and comparison with similar NMR data for related taxoids described in the literature. The stereochemistry of 56 was secured from an X-ray crystal structure determination of the 1,5-diol 57 produced from reduction of 56 with DIBAL.

  利用Bu3SnH-AIBN单独处理iodotrienedione 19和iododienynedione 38，可以通过串联自由基大环化-跨环自由基环化反应分别生成相应的紫杉烷环系25（25-30％）和56（50-60％）。相比之下，类似的一碘多烯酮61、63、65a、66a、86a和87a，以及相应的一碘烯二酮39a和59未能经历类似的串联自由基反应，而是直接还原这些底物中的碳-碘键，生成产物。紫杉烷类似物25和56的结构是通过分析它们的NMR光谱数据，并与文献中描述的相关紫杉烷的类似NMR数据进行比较来确定的。通过使用DIBAL还原56得到的1,5-二醇57的X射线晶体结构分析，确定了56的立体化学。
• Total Synthesis of the Calphostins:  Application of Fischer Carbene Complexes and Thermodynamic Control of Atropisomers
  作者：Craig A. Merlic、Courtney C. Aldrich、Jennifer Albaneze-Walker、Alan Saghatelian、Jerome Mammen

  DOI：10.1021/jo0014663

  日期：2001.2.1

  perylenequinones. Thermal equilibration to a 3:1 P:M atropisomeric ratio and separation of the perylenequinones followed by side chain desymmetrization and functionalization led to the total synthesis of enantio- and diastereomerically pure calphostin C in only twelve steps from commercially available starting materials. In addition, calphostins A, B, D, and several structural analogues were prepared to evaluate

  据报道有效的蛋白激酶C抑制剂钙磷蛋白A，B，C和D以及各种结构类似物的总合成。利用对映纯菲舍尔卡宾络合物的氨基苯甲酸酯化反应制备五取代的萘胺。优化侧链取代基后，将萘胺转化为邻萘醌，然后使用三氟乙酸和空气进行仿生氧化二聚，得到阻转异构体per醌的1：2 P / M混合物。热平衡至3：1 P：M的对映异构体比例，并分离出ylene醌，然后进行侧链去对称和官能化，仅用十二个步骤就可以从市售起始原料完全合成对映体和非对映体纯钙黄素C。此外，
• Preparation of deuterium-labeled monounsaturated and saturated fatty acids for use as stable isotope metabolic tracers
  作者：Sheldon N. Crane、Kevin Bateman、Sebastien Gagne、Jean-Francois Levesque

  DOI：10.1002/jlcr.1142

  日期：2006.12

  Synthetic routes adaptable to the preparation of a variety of d7-labeled monounsaturated and saturated fatty acids are reported. Using these reaction sequences, d7-oleic [18:1 (9c)], d7-elaidic [18:1 (9t)], and d7-stearic acid (18:0) were prepared for use in metabolism studies as stable isotope-labeled tracers. Copyright © 2006 John Wiley & Sons, Ltd.

  报道了一些适用于合成多种d7标记的单不饱和和饱和脂肪酸的合成路线。利用这些反应序列，制备了d7-油酸 [18:1 (9c)]、d7-艾拉酸 [18:1 (9t)] 和d7-硬脂酸 (18:0)，作为代谢研究中稳定同位素标记的示踪剂使用。版权 © 2006 John Wiley & Sons, Ltd.