(E)-1-octenyllithium | 110005-05-5

• 分子结构分类: 有机化合物 - 碳氢化合物衍生物
• 英文名称: (E)-1-octenyllithium
• 英文别名: (E)-octenyllithium；(E)-1-Lithio-1-octen；1-Lithio-1-trnas-octen；oct-1-en-t-yl-lithium；octenyllithium
• CAS: 110005-05-5
• 化学式: C₈H₁₅Li
• 分子量: 118.148
• InChiKey: PXPDRDIQJMSQFQ-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.57
• 重原子数：
  9
• 可旋转键数：
  5
• 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：

  (E)-1-octenyllithium 在 Saccharomyces cerevisiae 作用下， 生成 7-[(1S,2R,3R,5S)-3,5-Dihydroxy-2-((E)-oct-1-enyl)-cyclopentyl]-heptanoic acid
  参考文献：
  名称：

  前列腺素通过α-烷基环戊烯酮与有机铜的反应的立体特异性全合成。

  摘要：

  DOI：

  10.1021/ja00837a028
• 作为产物：
  描述：

  辛烯 在 2,5-二苯基-6a-硫杂并噻吩 、 zinc(II) chloride lithium 作用下， 以 四氢呋喃 为溶剂， 反应 24.0h， 以83.2%的产率得到(E)-1-octenyllithium
  参考文献：
  名称：

  Bogdanovic, Borislav; Wermeckes, Bernd, Angewandte Chemie, 1981, vol. 93, # 8, p. 691 - 693

  摘要：

  DOI：

文献信息

• Nickel- or palladium-catalyzed cross coupling. 31. Palladium- or nickel-catalyzed reactions of alkenylmetals with unsaturated organic halides as a selective route to arylated alkenes and conjugated dienes: scope, limitations, and mechanism
  作者：Eiichi Negishi、Tamotsu Takahashi、Shigeru Baba、David E. Van Horn、Nobuhisa Okukado

  DOI：10.1021/ja00242a024

  日期：1987.4

  Al, Zr, and Zn were 2, 3, and > 2000 mmol of (E)-1-octenylbenzene (8) per mmol of Pd(PPh/sub 3/)/sub 4/ per hour at room temperature, respectively. The stoichiometric reaction of PhPd(PPh/sub 3/)/sub 2/I (6) with 1.2 equiv of (E)-1-octenylzinc chloride (7) in a 2:1 mixture of CD/sub 2/Cl/sub 2/ and THF was examined in detail. The reaction follows second-order kinetics (k/sub 2/ = 2.9 L/(mol.min) at

  含有 Al、Zr 和 Zn 的立体和区域定义的烯基金属与芳基和烯基碘化物和溴化物在催化量的含有膦配体（如 PPh/sub 3/）的 Pd 或 Ni 配合物存在下反应，得到相应的交叉偶联产品。钯催化剂在烯基-芳基和烯基-烯基偶联反应中允许近 100% 的立体定向，而镍催化剂导致烯基-烯基偶联中的部分立体化学混乱。尽管还使用了许多其他金属，包括 Li、Mg、Cd、Hg、B、Si、Sn、Ti 和 Ce，但在本研究中使用的条件下，结果不如使用 Al、Zr 和 Zn 获得的结果。PhI 与 (E)-1-辛烯基金属（包含 Al、Zr 和 Zn）的钯催化反应的转换数为 2、3 和 > 在室温下，每小时每毫摩尔 Pd(PPh/sub 3/)/sub 4/ 分别为 2000 毫摩尔 (E)-1-辛烯基苯 (8)。PhPd(PPh/sub 3/)/sub 2/I (6) 与 1.2 当量 (E)-1-辛烯基氯化锌
• Asymmetric Synthesis of Less Accessible α-Tertiary Amines from Alkynyl <i>Z-</i> Ketimines
  作者：Taichi Kano、Yusuke Aota、Keiji Maruoka

  DOI：10.1002/anie.201710084

  日期：2017.12.18

  highly stereoselective synthesis of hitherto less accessible chiral α‐tertiary amines with multiple structurally similar linear carbon chains was achieved through chiral auxiliary mediated addition of organolithium reagents to the geometrically well‐controlled alkynyl Z‐ketimines. This stereoselective nucleophilic addition offers a general approach to the asymmetric synthesis of nitrogen‐containing

  通过手性辅助介导将有机锂试剂添加到几何形状良好控制的炔基Z-酮亚胺中，可以实现迄今为止难以获得的具有多个结构相似的线性碳链的手性α-叔胺的高度立体选择性合成。这种立体选择性亲核加成为含氮手性材料的不对称合成提供了一种通用方法。
• Palladium-catalyzed or -promoted reductive carbon-carbon coupling. Effects of phosphines and carbon ligands
  作者：Ei-ichi Negishi、Tamotsu Takahashi、Kazunari Akiyoshi

  DOI：10.1016/0022-328x(87)80048-7

  日期：1987.11

  The reaction of Cl2Pd(PEt3)2 with 2 equiv of (E)-t-BuCHCHLi, t-BuCCLi, or MeLi gives the corresponding R12Pd(PEt3)2 in a nearly quantitative yield without producing R1R1, where R1 = (E)-t-BuCHCH, t-BuCC, or Me. The reaction of PhLi or PhZnCl gives Ph2Pd(PEt3)2 and biphenyl in approximately 90 and 10% yields, respectively. On the other hand, the corresponding reaction of Cl2Pd(PPh3)2 produces R1R1

  Cl 2 Pd（PEt 3）2与2当量的（E）-t-BuCH = CHLi，t-BuC = CLi或MeLi的反应以几乎定量的产率得到相应的R 1 2 Pd（PEt 3）2而不产生R 1 R 1，其中R 1 =（E）-t-BuCH = CH，t-BuC = C或Me。PhLi或PhZnCl的反应分别以大约90％和10％的收率得到Ph 2 Pd（PEt 3）2和联苯。另一方面，Cl 2 Pd（PPh 3）2的相应反应在每种情况下，在1小时内产生的R 1 R 1的产率均> 95％。尝试检测R 1 2 Pd（PPh 3）2的尝试失败。从使用PEt 3，PPhMe 2和PPh 2 Me的情况可以推断出它们形成为不稳定的中间体。R 1 R 1的形成容易度与PR 3的碱度成反比，即，PEt 3＜PPhMe 2＜PPh 2 Me ＜PPh 3。尽管我2 Pd（PEt 3）2是顺式，在本研究中制备的所有其他R
• Synthesis of α-Substituted Allylic Amines via a Modified Bruylants Reaction
  作者：Claude Agami、François Couty、Gwilherm Evano

  DOI：10.1021/ol0059908

  日期：2000.7.1

  iminium ion promoter from alpha-amino nitriles, is an efficient additive in the Bruylants reaction involving vinylic Grignards. Improved yields of allylic amines were obtained when the starting alpha-amino nitrile was treated with this silver salt prior to its reaction with the vinylic Grignard. This improvement was not observed in the case of acetylenic Grignards. The reactivity of other vinyl organometallics

  四氟硼酸银，用作α-氨基腈的亚胺离子促进剂，在涉及乙烯基格氏试剂的Bruylants反应中是一种有效的添加剂。在这种银盐与乙烯基格氏试剂反应之前，用这种银盐处理起始的α-氨基腈，可以提高烯丙基胺的收率。在炔属格氏试剂中未观察到这种改善。简要检查了其他乙烯基有机金属（M = Zn，Li，Al，Cu，Si）的反应性。
• Preparation of polyfunctional diorganomercurials and their transmetallation to diorganozincs. Applications to the preparation of optically active secon
  作者：Michael J. Rozema、Duddu Rajagopal、Charles E. Tucker、Paul Knochel

  DOI：10.1016/0022-328x(92)88002-z

  日期：1992.10

  Two new methods of preparation of functionalized diorganomercurials have been developed. The first method involves a substitution reaction of (ICH2)2Hg with zinc-copper reagents FG-RCu(CN)ZnI in THF/DMF at - 60-degrees-C. Functional groups such as an ester, nitrile, ketone, phosphonate, halide, and boronic ester are tolerated in this reaction. The second method involves a reductive transmetallation between polyfunctional organozinc halides and mercurous chloride (Hg2Cl2). This very convenient procedure provides a rapid route to various functionalized diorganomercurials in good yields (61-89% yield). The synthetic utility of these mercury organometallics is demonstrated. Their transmetallation with zinc dust (toluene, 80-degrees-C, 3-5 h) affords dialkylzincs which add enantioselectively to aldehydes in the presence of a catalytic amount (20 mol%) of the norephedrine derivative 13. This transmetallation can also be used to prepare stereoselectively (E)-alkenylzinc halides (> 98% E). Addition of Cl(H)ZrCp2 to (E)-5-chloropentenylzinc bromide in CH2Cl2 (25-degrees-C, 1 min) affords a 1,1-bimetallic of zinc and zirconium Cl(CH2)4CH(ZnBr)ZrCp2(Cl) which reacts stereoselectively with an aldehyde providing the (E)-disubstituted olefin (49% yield; 100% E).