(E)-2-cyclohexyl-2-butene | 131436-21-0

• 分子结构分类: 有机化合物 - 碳氢化合物 - 不饱和烃
• 英文名称: (E)-2-cyclohexyl-2-butene
• 英文别名: [(E)-but-2-en-2-yl]cyclohexane
• CAS: 131436-21-0
• 化学式: C₁₀H₁₈
• 分子量: 138.253
• InChiKey: SOKZJAMQPSJUPA-YCRREMRBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.5
• 重原子数：
  10
• 可旋转键数：
  1
• 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)-2-cyclohexyl-2-butene 在 C₃₀H₄₂IrNOP⁽¹⁺⁾*C₃₂H₁₂BF₂₄^(1-) 、 氢气 作用下， 以 二氯甲烷 为溶剂， 23.0 ℃ 、500.01 kPa 条件下， 反应 2.0h， 生成 (S)-(-)-2-环己基丁烷
  参考文献：
  名称：

  铱催化的未官能化三烷基取代烯烃的不对称加氢反应

  摘要：

  具有双环吡啶基N，P配体的手性铱配合物已成为未官能化三烷基取代烯烃对映选择性加氢的有效催化剂。通过改变溶剂，压力和温度来优化反应条件，导致对映体过量高达99％。将（E）-2-环己基-2-丁烯和（E）-和（Z）-3,4-二甲基-2-戊烯这三种纯烯烃分别转化为相应的手性烷烃，分别为97％，94％和93 ％  ee， 分别。醋酸α-和γ-生育三烯基酯的三个C bondsC键的加氢导致醋酸α-和γ-生育酚酯具有非常高的非对映选择性。相同的催化剂已成功用于加氢取代带有γ位羧酸酯或酮基的三取代烯烃。该反应被用作关门菌西双螺旋菌的信息素的高度对映选择性合成中的关键步骤。结构类似的烯丙基醇的氢化也给出了高对映选择性。

  DOI：

  10.1002/asia.201000595
• 作为产物：
  描述：

  r-4-cyclohexyl-t-3,4-dimethyloxetan-2-one 在 silica gel 作用下， 以95%的产率得到(E)-2-cyclohexyl-2-butene
  参考文献：
  名称：

  A practical and efficient method for the synthesis of .beta.-lactones

  摘要：

  This paper describes a convenient one-step preparation of beta-lactones based on the addition of thiol ester enolates to carbonyl compounds. Under the proper conditions the resulting aldolates undergo spontaneous cyclization to produce beta-lactones in good to excellent yield. The new beta-lactone synthesis provides access to 2-oxetanones with a variety of substituents and substitution patterns. In general, thiol ester enolates combine with carbonyl compounds to form the less sterically crowded beta-lactone diastereomers, and in some cases the reaction proceeds with excellent stereoselectivity. In conjunction with the stereospecific decarboxylation of beta-lactones, this chemistry also provides a very attractive approach to the synthesis of substituted alkenes.

  DOI：

  10.1021/jo00003a047

文献信息

• Wittig ethylidenation of ketones: reagent control of Z/E selectivity
  作者：E. Vedejs、J. Cabaj、M. J. Peterson

  DOI：10.1021/jo00075a064

  日期：1993.11
• DANHEISER, RICK L.;NOWICK, JAMES S., J. ORG. CHEM., 56,(1991) N, C. 1176-1185
  作者：DANHEISER, RICK L.、NOWICK, JAMES S.

  DOI：——

  日期：——
• Observation of Pseudorotamers of Two Unconstrained Wittig Intermediates, (3<i>RS</i>,4<i>SR</i>)- and (3<i>RS</i>,4<i>RS</i>)-4-Cyclohexyl-2-ethyl-3,4- dimethyl-2,2-diphenyl-1,2λ⁵-oxaphosphetane, by Dynamic ³¹P NMR Spectroscopy:  Line-Shape Analyses, Conformations, and Decomposition Kinetics
  作者：Felix Bangerter、Martin Karpf、Lukas A. Meier、Paul Rys、Peter Skrabal

  DOI：10.1021/ja974332o

  日期：1998.10.1

  The two typical, that is unstabilized and unconstrained, oxaphosphetane diastereomers (3RS,4SR)- (3) and (3RS,4RS)-4-cyclohexyl-2-ethyl-3,4-dimethyl-2,2-diphenyl-1,2 lambda(5)-oxaphosphetane (5) have been prepared selectively by deprotonation of (1RS,2SR)- (6) and (1RS,2RS)-(2-cyclohexyl-2-hydroxy-1-methylpropyl)-ethyldiphenylphosphonium iodide (7). The X-ray structure analysis of 7 established the relative configurations of 6 and 7 and consequently those of 3 and 5. Pseudorotation of the 1,2-oxaphosphetanes 3 and 5 and their alkene formations have been studied by P-31 NMR spectroscopy. The conformations of the resolved pseudorotamers at the pentacoordinate trigonal bipyramidal phosphorus atom are identified by H-1,C-13,and 31P NMR data. For both diastereomers, the two rotamers with equatorial position of the ethyl substituent dominate in pseudorotation. Line-shape analyses provided the rate constants and activation parameters of pseudorotations. The results represent the first experimental data for pseudorotation of unstabilized and unconstrained I,2-oxaphosphetanes Oxaphosphetanes 3 and 5 stereoselectively decompose to (Z)- and (E)-2-cyclohexylbut-2-ene, respectively. At -30 degrees C, pseudorotations are faster than alkene formations by a factor of ca. 10(11), and at -20 degrees C, the half-life of the trans isomer 5 in alkene formation is approximately 8 times longer than that of the cis isomer 3.
• A practical and efficient method for the synthesis of .beta.-lactones
  作者：Rick L. Danheiser、James S. Nowick

  DOI：10.1021/jo00003a047

  日期：1991.2

  This paper describes a convenient one-step preparation of beta-lactones based on the addition of thiol ester enolates to carbonyl compounds. Under the proper conditions the resulting aldolates undergo spontaneous cyclization to produce beta-lactones in good to excellent yield. The new beta-lactone synthesis provides access to 2-oxetanones with a variety of substituents and substitution patterns. In general, thiol ester enolates combine with carbonyl compounds to form the less sterically crowded beta-lactone diastereomers, and in some cases the reaction proceeds with excellent stereoselectivity. In conjunction with the stereospecific decarboxylation of beta-lactones, this chemistry also provides a very attractive approach to the synthesis of substituted alkenes.
• Iridium-Catalyzed Asymmetric Hydrogenation of Unfunctionalized, Trialkyl-Substituted Olefins
  作者：Aie Wang、Rui P. A. Fraga、Esther Hörmann、Andreas Pfaltz

  DOI：10.1002/asia.201000595

  日期：2011.2.1

  Chiral iridium complexes with bicyclic pyridine‐based N,P ligands have emerged as efficient catalysts for the enantioselective hydrogenation of unfunctionalized trialkyl‐substituted olefins. Optimization of the reaction conditions by variation of the solvent, pressure, and temperature led to enantiomeric excesses of up to 99 %. Three pure alkenes, (E)‐2‐cyclohexyl‐2‐butene and (E)‐ and (Z)‐3,4‐dimethyl‐2‐pentene

  具有双环吡啶基N，P配体的手性铱配合物已成为未官能化三烷基取代烯烃对映选择性加氢的有效催化剂。通过改变溶剂，压力和温度来优化反应条件，导致对映体过量高达99％。将（E）-2-环己基-2-丁烯和（E）-和（Z）-3,4-二甲基-2-戊烯这三种纯烯烃分别转化为相应的手性烷烃，分别为97％，94％和93 ％  ee， 分别。醋酸α-和γ-生育三烯基酯的三个C bondsC键的加氢导致醋酸α-和γ-生育酚酯具有非常高的非对映选择性。相同的催化剂已成功用于加氢取代带有γ位羧酸酯或酮基的三取代烯烃。该反应被用作关门菌西双螺旋菌的信息素的高度对映选择性合成中的关键步骤。结构类似的烯丙基醇的氢化也给出了高对映选择性。