4-tert-butyldimethylsilyloxy-1-decene | 129286-13-1

• 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: 4-tert-butyldimethylsilyloxy-1-decene
• 英文别名: Tert-butyl-dec-1-en-4-yloxy-dimethylsilane
• CAS: 129286-13-1
• 化学式: C₁₆H₃₄OSi
• 分子量: 270.531
• InChiKey: JITNZDZFQLUXCT-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.92
• 重原子数：
  18
• 可旋转键数：
  10
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.88
• 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：

  4-tert-butyldimethylsilyloxy-1-decene 在 Wilkinson's catalyst 劳森试剂 、 六甲基磷酰三胺 、 lithium hydroxide 、 二甲基硫 、 PySSpy 、 四丁基氟化铵 、 氢气 、 sodium hexamethyldisilazane 、 silver perchlorate 、 臭氧 、 三苯基膦 作用下， 以 四氢呋喃 、 甲醇 、 甲苯 、 苯 为溶剂， 反应 50.5h， 生成 (+/-)-8-hexyl-2-oxocanethione
  参考文献：
  名称：

  从硫代内酯合成中等大小的环醚。在聚醚合成中的应用

  摘要：

  已经制备了多种中等大小的硫代内酯，并与亲核试剂缩合，在用甲基碘淬灭后得到烷基化硫代缩醛。在自由基条件下使用三苯基氢化锡进行还原脱硫可以快速有效地提供相应的环醚，并且在大多数情况下具有完全立体控制。该方法已通过构建短杆菌毒素 A (1) 的 B 环和 D 环模型系统以及 (±)-lauthisan 的合成得到证明

  DOI：

  10.1021/ja00173a013
• 作为产物：
  描述：

  dec-1-en-4-ol 、 叔丁基二甲基氯硅烷 在 咪唑 作用下， 以 二氯甲烷 为溶剂， 生成 4-tert-butyldimethylsilyloxy-1-decene
  参考文献：
  名称：

  RuHCl(CO)(PPh3)3-催化高烯丙基硅醚和碳酸酯异构化为烯丙基硅醚和碳酸酯

  摘要：

  以RuHCl(CO)(PPh 3 ) 3为催化剂，研究了高烯丙基甲硅烷基醚和碳酸酯的选择性烯烃异构化反应。虽然在氧原子 α 位的芳基或烷基取代基导致选择性转化为烯丙基甲硅烷基醚，但在 α 位没有取代基导致异构化为烯醇甲硅烷基醚。相反，无论 α 位的取代基如何，高烯丙基碳酸酯的异构化都会选择性地生成相应的碳酸烯丙酯。

  DOI：

  10.1002/adsc.202201394

文献信息

• Investigations of the Scope and Mechanism of the Tandem Hydroesterification/Lactonization Reaction
  作者：Lijun Wang、Paul E. Floreancig

  DOI：10.1021/ol048378f

  日期：2004.11.1

  alcohols and 2-pyridylmethyl formate in the presence of Ru(3)(CO)(12) initiates a tandem sequence of hydroesterification and lactonization. Mechanistic studies suggest that regioselectivity and overall reaction efficiency are governed by the relative rates of reductive elimination and beta-hydride elimination for the alkylruthenium intermediates.

  在Ru（3）（CO）（12）存在的情况下加热烯丙基和均烯丙基醇和甲酸2-吡啶基甲基甲酸酯可引发氢化酯化和内酯化的串联序列。机理研究表明，区域选择性和整体反应效率受烷基钌中间体的相对消除和β-氢化物消除的相对速率支配。
• PhSeSiR₃-Catalyzed Group Transfer Radical Reactions
  作者：Ganesh Pandey、K. S. S. P. Rao、K. V. Nageshwar Rao

  DOI：10.1021/jo000128z

  日期：2000.7.1

  A novel design for initiating radical-based chemistry in a catalytic fashion is described. The design of the concept is based on the phenylselenyl group transfer reaction from alkyl phenyl selenides by utilizing PhSeSiR3 (1) as a catalytic reagent. The reaction is initiated by the homolytic cleavage of -C-Se- bond of an alkyl phenyl selenide by the in situ generated alkylsilyl radical (R3Si.), obtained by the mesolysis of PhSeSiR3](.-) (1(.-)). The oxidative dimerization of counteranion PhSe- to PhSeSePh functions as radical terminator. The generation of 1(.-) is achieved by the photoinduced electron transfer (PET) promoted reductive activation of 1 through a photosystem comprising of a visible-light (410 nm)-absorbing electron rich DMA as an electron donor and ascorbic acid as a co-oxidant (Figure 1). The optimum mole ratio between the catalyst 1 and alkyl phenyl selenides for successful reaction is established to be 1:10. The generality of the concept is demonstrated by carrying out variety of radical reactions such as cyclization (10, 15-18), intermolecular addition (25), and tandem annulations (32).
• Generation and Mesolysis of PhSeSiR₃]^•-:  Mechanistic Studies by Laser Flash Photolysis and Application for Bimolecular Group Transfer Radical Reactions
  作者：Ganesh Pandey、K. S. Sesha Poleswara Rao、D. K. Palit、J. P. Mittal

  DOI：10.1021/jo972345e

  日期：1998.6.1

  The investigation presented in this paper explores the mechanistic aspects and synthetic potentials of PET promoted reductive activation of selenosilane la to its radical anion la(-.). PET activation of la is achieved through a photosystem comprising a light-absorbing electron-rich aromatic (ERA), such as DMN or DMA, as an electron donor and ascorbic acid as a co-oxidant. The evidence for the ET from excited singlet states of DMN as well as DMA to la is suggested by estimating negative Delta G(et) (-51 and -43.46 kcal mol(-1), respectively) values and nearly diffusion-controlled fluorescence quenching rate constants (k(q)TR) 0.36 x 10(10) M-1 s(-1) and 0.28 x 10(10) M-1 s(-1), respectively, from time-resolved fluorescence quenching study. The transient absorption spectra of DMN.+, DMA(.+), and la(.-) are obtained initially by pulse radiolysis in order to correlate the time-resolved absorption spectral data. Laser flash photolysis studies in the nanosecond time domain have confirmed the generation of la(.-), DMN.+, and DMA(.+), supporting the participation of the triplet state of DMN or DMA in the ET reaction. Mesolytic cleavage of 1a(.-) produced a silyl radical and a phenyl selenide anion. The preparative PET activation of la in acetonitrile in the presence of DMN or DMA leads to the formation of 5 and 6, confirming the fragmentation pattern of la(.-). The overall ET rate constants (K-r(DMN) = 0.99 x 10(10) M-1 s(-1) and k(r)(DMA) = 1.62 x 10(10) M-1 s(-1)) and limiting quantum yields (phi(lim)DMN) = 0.034 and phi(lim)(DMA) = 0.12) are estimated from the inverse plot (1/[la] vs 1/phi(dis)) Obtained by measuring the dependence of photodissociation quantum yields of la at its maximum concentration in the presence of DMN or DMA. Silicon-centered radical species generated from the mesolysis of la(.-) are utilized for initiating a radical reaction by the abstraction of halogen atom from -C-X (X = Cl, Br) bonds, while PhSe- terminates the radical sequences via PhSeSePh. This concept is successfully applied for the bimolecular group transfer (BMGT) radical reactions and intermolecular radical chain addition reactions.
• Synthesis of medium-sized ring ethers from thionolactones. Applications to polyether synthesis
  作者：K. C. Nicolaou、D. G. McGarry、P. K. Somers、B. H. Kim、W. W. Ogilvie、G. Yiannikouros、C. V. C. Prasad、C. A. Veale、R. R. Hark

  DOI：10.1021/ja00173a013

  日期：1990.8

  Reductive desulfurization using triphenyltin hydride under radical conditions afforded the corresponding cyclic ethers rapidly and efficiently and, in most cases, with complete stereocontrol. This methodology has been proven through the construction of model systems of rings B and D of brevetoxin A (1) and a synthesis of (±)-lauthisan

  已经制备了多种中等大小的硫代内酯，并与亲核试剂缩合，在用甲基碘淬灭后得到烷基化硫代缩醛。在自由基条件下使用三苯基氢化锡进行还原脱硫可以快速有效地提供相应的环醚，并且在大多数情况下具有完全立体控制。该方法已通过构建短杆菌毒素 A (1) 的 B 环和 D 环模型系统以及 (±)-lauthisan 的合成得到证明
• RuHCl(CO)(PPh<sub>3</sub>)<sub>3</sub>‐Catalyzed Isomerization of Homoallyl Silyl Ethers and Carbonates to Allyl Silyl Ethers and Carbonates
  作者：Takahide Fukuyama、Takashi Kuwahara、Yuki Yamamoto、Baptiste Picard、Ilhyong Ryu

  DOI：10.1002/adsc.202201394

  日期：——

  The selective olefin isomerization of homoallyl silyl ethers and carbonates was studied using RuHCl(CO)(PPh3)3 as a catalyst. While an aryl or alkyl substituent at the α-position to the oxygen atom caused the selective conversion to allyl silyl ethers, no substituent at the α-position resulted in the isomerization to enol silyl ethers. In contrast, the isomerization of homoallyl carbonates gave the

  以RuHCl(CO)(PPh 3 ) 3为催化剂，研究了高烯丙基甲硅烷基醚和碳酸酯的选择性烯烃异构化反应。虽然在氧原子 α 位的芳基或烷基取代基导致选择性转化为烯丙基甲硅烷基醚，但在 α 位没有取代基导致异构化为烯醇甲硅烷基醚。相反，无论 α 位的取代基如何，高烯丙基碳酸酯的异构化都会选择性地生成相应的碳酸烯丙酯。