cis-2-Vinylcyclopropanmethanol | 206982-01-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: cis-2-Vinylcyclopropanmethanol
• 英文别名: [(1R,2R)-2-ethenylcyclopropyl]methanol
• CAS: 206982-01-6
• 化学式: C₆H₁₀O
• 分子量: 98.1448
• InChiKey: BBEUBSMPIQDNHL-WDSKDSINSA-N

物化性质

• 沸点：
  129.5±9.0 °C(Predicted)
• 密度：
  1.059±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.8
• 重原子数：
  7
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  cis-2-Vinylcyclopropanmethanol 在 吡啶 、 二甲基硫 、 臭氧 作用下， 以 二氯甲烷 为溶剂， 反应 3.42h， 生成 Benzoic acid (1R,2S)-2-formyl-cyclopropylmethyl ester
  参考文献：
  名称：

  Controlling π-Facial Diastereoselectivity in the 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Pentenoates and Furanones:  Enantioselective Stereodivergent Syntheses of Cyclopropane Hydroxy Acids and Didehydro Amino Acids

  摘要：

  The title compounds have been synthesized in both enantiomeric forms and in good overall yields by using D-glyceraldehyde as the single chiral precursor. The efficiency and usefulness of the synthetic routes have been secured by performing controlled manipulations of the functional groups and by highly stereoselective transformations, namely Wittig-Horner condensations and cyclopropanations. Cyclopropane derivatives have been synthesized through 1,3-dipolar cycloaddition of diazomethane to chiral pentenoates or furanones obtained, in turn, from D-glyceraldehyde. Syn/anti stereochemistry of the cycloadducts has been unequivocally assigned and rationalized. Since pi-facial diastereoselectivity involved in these cycloadditions is the opposite for cyclic and open-chain structures, enantiomeric series of products can be derived.

  DOI：

  10.1021/jo972219a
• 作为产物：
  描述：

  (5S)-5-(hydroxymethyl)-5H-furan-2-one 在 吡啶 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 二异丁基氢化铝 、 溶剂黄146 、 sodium iodide 、 锌 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 丙酮 、 甲苯 为溶剂， 反应 32.17h， 生成 cis-2-Vinylcyclopropanmethanol
  参考文献：
  名称：

  Controlling π-Facial Diastereoselectivity in the 1,3-Dipolar Cycloadditions of Diazomethane to Chiral Pentenoates and Furanones:  Enantioselective Stereodivergent Syntheses of Cyclopropane Hydroxy Acids and Didehydro Amino Acids

  摘要：

  The title compounds have been synthesized in both enantiomeric forms and in good overall yields by using D-glyceraldehyde as the single chiral precursor. The efficiency and usefulness of the synthetic routes have been secured by performing controlled manipulations of the functional groups and by highly stereoselective transformations, namely Wittig-Horner condensations and cyclopropanations. Cyclopropane derivatives have been synthesized through 1,3-dipolar cycloaddition of diazomethane to chiral pentenoates or furanones obtained, in turn, from D-glyceraldehyde. Syn/anti stereochemistry of the cycloadducts has been unequivocally assigned and rationalized. Since pi-facial diastereoselectivity involved in these cycloadditions is the opposite for cyclic and open-chain structures, enantiomeric series of products can be derived.

  DOI：

  10.1021/jo972219a

文献信息

• Palladium-Promoted Neutral 1,4-Brook Rearrangement/Intramolecular Allylic Cyclization Cascade Reaction: A Strategy for the Construction of Vinyl Cyclobutanols
  作者：Hao Zhang、Shiqiang Ma、Ziyun Yuan、Peng Chen、Xingang Xie、Xiaolei Wang、Xuegong She

  DOI：10.1021/acs.orglett.7b01381

  日期：2017.7.7

  cascade reaction to build vinyl cyclobutanol rings through activation of vinyl epoxides by palladium, followed by 1,4-Brook rearrangement and intramolecular cyclization with a palladium complex of the resulting carbon anion, is described. Through this cascade reaction, several highly substituted cyclobutanol substrates were achieved in good yields with high stereoselectivities.

  描述了一种级联反应，该级联反应通过钯活化乙烯基环氧化物，然后进行1,4-Brook重排和与所得碳阴离子的钯配合物进行分子内环化，从而构建乙烯基环丁醇环。通过该级联反应，以高收率和高立体选择性获得了几种高度取代的环丁醇底物。
• Rh(I)-Catalyzed Intramolecular [3 + 2] Cycloaddition of <i>trans</i>-Vinylcyclopropane-enes
  作者：Lei Jiao、Siyu Ye、Zhi-Xiang Yu

  DOI：10.1021/ja8008715

  日期：2008.6.1

  Vinylcyclopropane (VCP) has been well applied as a five-carbon component, rather than a three-carbon component, in transition-metal catalyzed cycloadditions. Here we demonstrate a Rh(I)-catalyzed [3 + 2] reaction of trans-VCP-enes, where VCP acts as a three-carbon synthon to furnish five-membered carbocycles. This novel cycloaddition is efficient in generating bicyclic cyclopentanes in good yields

  在过渡金属催化的环加成反应中，乙烯基环丙烷 (VCP) 已被很好地用作五碳组分，而不是三碳组分。在这里，我们展示了 Rh(I) 催化的反式 VCP-烯的 [3 + 2] 反应，其中 VCP 作为三碳合成子提供五元碳环。这种新颖的环加成可以有效地从简单且易于制备的底物以良好的产率生成双环环戊烷。当使用顺式 VCP-ene 作为底物时，VCP 作为一个五碳单元产生 [5 + 2] 环加合物。已经提出了 VCP-烯的 [3 + 2] 和 [5 + 2] 环加成的合理化。
• Reaction of Organoaluminium Reagents with Cyclopropylmethyl Acetates and 2-Vinylcyclopropane-1,1-dicarboxylate Esters
  作者：Tamejiro Hiyama、Yoshitomi Morizawa、Hajime Yamamoto、Hitosi Nozaki

  DOI：10.1246/bcsj.54.2151

  日期：1981.7

  Alkylation of trans-1-(1-acetoxy-3-phenylpropyl)-2-vinylcyclopropane with trialkylaluminium proceeds under regioselective ring-opening to give 3-alkylated trans-8-phenyl-1,5-octadiene (selectivity 73–83%). The regio- and stereochemistry of homoconjugate addition to activated vinylcyclopropanes having a doubly carbonyl substituted ring carbon was studied. Trialkylaluminium on addition to diethyl 2-vinylcyclopropane-1

  研究了环丙基甲基乙酸酯的开环烷基化。7-（1-乙酰氧基庚基）降卡烷的乙酰氧基在用三烷基铝处理后被烷基取代，但反式-1-（1-乙酰氧基乙基）-2-苯基环丙烷与三烷基铝的烷基化产生反式-5-苯基- 2-烯烃。(1S,2S)-2-苯基环丙基甲基乙酸酯与三甲基铝的反应导致光学活性完全丧失，得到外消旋4-苯基-1-戊烯。在区域选择性开环下，反式-1-(1-乙酰氧基-3-苯基丙基)-2-乙烯基环丙烷与三烷基铝的烷基化反应得到 3-烷基化的反式-8-苯基-1,5-辛二烯（选择性 73-83%） . 研究了具有双羰基取代的环碳的活化乙烯基环丙烷的同共轭加成的区域和立体化学。三烷基铝以 1,5-方式加入 2-乙烯基环丙烷-1,1-二羧酸二乙酯后，得到（2-烷基-3-丁烯基）丙二酸二乙酯（选择性超过 96%）。相反...
• Cascade Cope/Winstein Rearrangements: Synthesis of Azido-Cycloheptadienes from Dialkenylcyclopropanes Possessing a Vinyl Azide
  作者：Thomas Abegg、Janine Cossy、Christophe Meyer

  DOI：10.1021/acs.orglett.2c01888

  日期：2022.7.15

  2-Dialkenylcyclopropanes incorporating a vinyl azide, generated by Knoevenagel condensations between the corresponding cyclopropanecarbaldehydes and α-azido ketones, undergo cascade Cope and Winstein [3,3]-sigmatropic rearrangements, under mild conditions. The sequence allows access to diversely substituted 1,4-cycloheptadienes armed with a secondary allylic azide with up to three stereocenters.

  顺式-1,2-二烯基环丙烷包含乙烯基叠氮化物，由相应的环丙烷甲醛和 α-叠氮基酮之间的 Knoevenagel 缩合产生，在温和条件下发生级联 Cope 和 Winstein [3,3]-σ 重排。该序列允许使用具有多达三个立体中心的二级烯丙基叠氮化物的多种取代的 1,4-环庚二烯。
• Rh(I)-Catalyzed [5 + 1] Cycloaddition of Vinylcyclopropanes and CO for the Synthesis of α,β- and β,γ-Cyclohexenones
  作者：Guo-Jie Jiang、Xu-Fei Fu、Qian Li、Zhi-Xiang Yu

  DOI：10.1021/ol2031526

  日期：2012.2.3

  A cationic Rh(I)-catalyzed [5 + 1] cycloaddition of vinylcyclopropanes and CO has been developed, affording either beta,gamma-cyclohexenones as major products or alpha,beta-cyclohexenones exclusively, under different reaction conditions.