(E)-(4-chlorobut-2-en-2-yl)cyclohexane | 1311260-16-8

• 分子结构分类: 有机化合物 - 有机卤素化合物 - 有机氯化物
• 英文名称: (E)-(4-chlorobut-2-en-2-yl)cyclohexane
• 英文别名: [(E)-4-chlorobut-2-en-2-yl]cyclohexane
• CAS: 1311260-16-8
• 化学式: C₁₀H₁₇Cl
• 分子量: 172.698
• InChiKey: ZMTAGSRQOQOKQT-VQHVLOKHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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)-(4-chlorobut-2-en-2-yl)cyclohexane 、 频那醇硼烷 在 magnesium 作用下， 以 四氢呋喃 为溶剂， 反应 4.0h， 以96%的产率得到2-(2-cyclohexylbut-3-en-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane
  参考文献：
  名称：

  Congested C–C Bonds by Pd-Catalyzed Enantioselective Allyl–Allyl Cross-Coupling, a Mechanism-Guided Solution

  摘要：

  Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3'-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.

  DOI：

  10.1021/ja502280w
• 作为产物：
  描述：

  乙酰基环己烷 在 氯化亚砜 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 3.0h， 生成 (E)-(4-chlorobut-2-en-2-yl)cyclohexane
  参考文献：
  名称：

  Congested C–C Bonds by Pd-Catalyzed Enantioselective Allyl–Allyl Cross-Coupling, a Mechanism-Guided Solution

  摘要：

  Under the influence of a chiral bidentate diphosphine ligand, the Pd-catalyzed asymmetric cross-coupling of allylboron reagents and allylic electrophiles establishes 1,5-dienes with adjacent stereocenters in high regio- and stereoselectivity. A mechanistic study of the coupling utilizing reaction calorimetry and density functional theory analysis suggests that the reaction operates through an inner-sphere 3,3'-reductive elimination pathway, which is both rate-defining and stereodefining. Coupled with optimized reaction conditions, this mechanistic detail is used to expand the scope of allyl allyl couplings to allow the generation of 1,5-dienes with tertiary centers adjacent to quaternary centers as well as a unique set of cyclic structures.

  DOI：

  10.1021/ja502280w

文献信息

• Enantioselective Construction of All-Carbon Quaternary Centers by Branch-Selective Pd-Catalyzed Allyl–Allyl Cross-Coupling
  作者：Ping Zhang、Hai Le、Robert E. Kyne、James P. Morken

  DOI：10.1021/ja2039248

  日期：2011.6.29

  The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3'-reductive elimination of bis(η(1)-allyl)palladium intermediates. Strategies for distinguishing the

  描述了外消旋叔烯丙基碳酸酯和烯丙基硼酸酯的 Pd 催化交叉偶联。该反应以高度区域选择性和对映选择性方式生成全碳四元中心。这些反应的结果与通过双 (η(1)-烯丙基) 钯中间体的 3,3'-还原消除方式进行的过程一致。还描述了区分产物烯烃的策略和在 (+)-α-cuparenone 合成中的应用。
• Process for the preparation of alkenyl cyanoacetates
  申请人：SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

  公开号：EP0001847A1

  公开（公告）日：1979-05-16

  Process for the preparation of a cyanoacetate having the following general formula: wherein each of the symbols R1 and R2 represents an alkyl group or a cycloalkyl group, by contacting cyanoacetic acid with an alkenyl halide of the general formula: wherein R' and R2 have the same meaning as defined hereinbefore and Hal represents a halogen atom having an atomic number of at least 17, in the presence of a hydrogen-halide acceptor and a substantially inert organic solvent. The compounds of formula (I) are intermediates having uses in the manufacture of pyrethroid insecticides and other compounds.

  具有以下通式的氰基乙酸酯的制备方法 其中符号 R1 和 R2 各代表一个烷基或环烷基，通过将氰基乙酸与通式为 其中 R' 和 R2 的含义与前文定义相同，Hal 代表原子序数至少为 17 的卤原子，在氢卤受体和基本惰性的有机溶剂存在下进行。式（I）化合物是中间体，可用于制造拟除虫菊酯杀虫剂和其他化合物。
• US4169105A
  申请人：——

  公开号：US4169105A

  公开（公告）日：1979-09-25