(+/-)-4-methylene-5-hexen-2-ol | 71885-98-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (+/-)-4-methylene-5-hexen-2-ol
• 英文别名: 4-methylene-5-hexene-2-ol；4-methylene-5-hexen-2-ol；2-vinyl-1-penten-4-ol；4-methylene-hex-5-en-2-ol；4-methylidenehex-5-en-2-ol
• CAS: 71885-98-8
• 化学式: C₇H₁₂O
• 分子量: 112.172
• InChiKey: HHQQFJVNLOLQAM-UHFFFAOYSA-N

物化性质

• 沸点：
  66-70 °C(Press: 45 Torr)
• 密度：
  0.850±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  8
• 可旋转键数：
  3
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 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：

  (+/-)-4-methylene-5-hexen-2-ol 在 吡啶 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 甲苯 、 苯 为溶剂， 反应 97.0h， 生成 4-Allyl-1,2,3,6-tetrahydro-N-phenylphthalimid
  参考文献：
  名称：

  Double Diels-Alder Reaction oftrans-3-Methylene-1,4-hexadiene and 1-Methyl-3-methylene-4-pentenyl Tosylate

  摘要：

  通过 1-甲基-3-亚甲基-4-戊烯对甲苯磺酸盐，可以从氯丁二烯和甲基环氧乙烷的格氏试剂中获得交叉共轭的三烯，即反式-3-亚甲基-1,4-己二烯。研究了三烯的二烯透射 Diels-Alder 反应和对甲苯磺酸盐的双 Diels-Alder 反应的逐步顺序。讨论了这些反应在路易斯酸催化剂存在或不存在的情况下的立体选择性和区域选择性。

  DOI：

  10.1246/bcsj.59.1869
• 作为产物：
  描述：

  四氢-2-甲基-4-亚甲基-2H-吡喃 在 正丁基锂 、 potassium tert-butylate 、 二异丙胺 作用下， 以86%的产率得到(+/-)-4-methylene-5-hexen-2-ol
  参考文献：
  名称：

  1,2-Elimination of alcohol from homoallyl ethers under the influence of mixed metal bases

  摘要：

  DOI：

  10.1016/s0040-4020(01)82022-6

文献信息

• Chiral synthesis VIA organoboranes. 26. An efficient synthesis of isoprenyl derivatives of borane - valuable reagents for the isoprenylboration of aldehydes. A convenient route to both enantiomers of ipsenol and ipsdienol in high optical purity
  作者：Herbert C. Brown、Ramnarayan S. Randad

  DOI：10.1016/s0040-4020(01)85575-7

  日期：1990.1

  namely metallation of isoprene with potassium 2,2,5,5-tetramethylpiperidide followed by sequential treatment with B-methoxydialkylborane and boron trifluoride-etherate. These reagents are used for the convenient isoprenylation of aldehydes. Reaction of isovaleraldehyde and β, β-dimethylacrolein with B2'isoprenyldiisopinocampheylborane provides both ipsenol and ipsdienol, respectively in 65% yields and 96%

  B-异戊二烯基二烷基硼烷的制备是通过采用Schlosser程序的Brandsma改性完成的，即用2,2,5,5-四甲基哌啶钾对异戊二烯进行金属化，然后依次用B-甲氧基二烷基硼烷和三氟化硼-醚化物处理。这些试剂用于方便的醛异戊二烯化。异戊醛和β，β-二甲基丙烯醛与B 2'异戊二烯基二异辛基环戊基硼烷的反应分别提供了ipsenol和ipsdienol，产率为65％，ee为96％。
• 2-dipropylborylmethyl-1,3-butadiene - a new reagent for isoprenylation. Efficient synthesis of ipsenol and ipsdienol
  作者：Yuri N. Bubnov、Marina Yu. Etinger

  DOI：10.1016/s0040-4039(00)94915-3

  日期：1985.1

  A simple and convenient method for isoprenylation of carbonyl compounds and ethoxyacetylene using the titled new boron containing “isoprene C-5 synthon” and application of this efficient procedure to the synthesis of ipsenol and ipsdienol are described.

  描述了一种简单，方便的方法，该方法使用标题为“硼异戊二烯C-5合成子”的新型硼对羰基化合物和乙氧基乙炔进行异戊二烯化，并将该有效方法应用于ipsenol和ipsdienol的合成。
• Chemistry of dioxenium cations. Synthetic and mechanistic studies on the stereocontrolled formation of tetrahydropyrans from homoallylic alcohols and ortho esters
  作者：Francoise Perron-Sierra、Michele A. Promo、Van A. Martin、Kim F. Albizati

  DOI：10.1021/jo00021a043

  日期：1991.10

  Despite their long history, dioxenium cations are underutilized reactive synthetic intermediates. It was found that ortho esters and homoallylic alcohols in the presence of Lewis acids provide 4-heterosubstituted pyranosides in a stereoselective manner. The mechanistic course of events was supported by control experiments and synthesis of a putative mixed ortho ester intermediate which exhibited identical reactivity. A transition state for termination of the dioxenium cation-olefin cyclization is proposed, involving intramolecular delivery of chloride by a coordinated tin species. Structure-reactivity relationships indicate that a cation-stabilizing substituent (alkyl or alkoxy) at the internal position of the olefin is required for cyclization. A variety of 3-alkyl-substituted homoallylic alcohols cyclize cleanly to substituted 2-alkoxytetrahydropyrans in good yield. beta-silyloxy silyl enol ethers were found to smoothly provide 4-oxotetrahydropyranosides when subjected to the same reaction conditions. For these substrates, the course of the cyclization proceeds in a different manner involving a rapid intermolecular Mukaiyama aldol condensation followed by transacetalization.
• Isoprenylation of carbonyl compounds, esters, and alkoxyacetylenes with 2-dipropylborylmethyl-1,3-butadiene and the synthesis of ipsenol and ipsdienol
  作者：Yu. N. Bubnov、M. Yu. �tinger、A. V. Ignatenko

  DOI：10.1007/bf00957158

  日期：1989.6
• A regio- and stereocontrolled access to 2,4-dienols by amide/alcoholate-promoted ring-opening of dihydro-pyrans
  作者：Christian Margot、Manfred Schlosser

  DOI：10.1016/s0040-4039(00)98505-8

  日期：1985.1