(2,2-二甲基螺[2.4]庚-4,6-二烯-1-基)甲醇 | 126899-48-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: (2,2-二甲基螺[2.4]庚-4,6-二烯-1-基)甲醇
• 英文名称: 2,2-dimethyl-1-hydroxymethylspiro<2,4>hepta-4,6-diene
• 英文别名: (2,2-Dimethylspiro[2.4]hepta-4,6-dien-1-yl)methanol
• CAS: 126899-48-7
• 化学式: C₁₀H₁₄O
• 分子量: 150.221
• InChiKey: OIWFEDWZNZFNPL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  11
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  (2,2-二甲基螺[2.4]庚-4,6-二烯-1-基)甲醇 在 MnO₂ on activated carbon 、 cadmium(II) chloride 、 lithium diisopropyl amide 作用下， 反应 2.5h， 生成 (+)-(5R,1'R)-3-Methyl-5-(2',2'-dimethylspiro<2.4>hepta-4',6'-dien-1'-yl)-6-oxa-2-cyclohexenone
  参考文献：
  名称：

  Lei, Bo; Fallis, Alex G., Journal of the American Chemical Society, 1990, vol. 112, # 11, p. 4609 - 4610

  摘要：

  DOI：
• 作为产物：
  描述：

  环戊二烯 在 四氢吡咯 作用下， 以 甲醇 为溶剂， 生成 (2,2-二甲基螺[2.4]庚-4,6-二烯-1-基)甲醇
  参考文献：
  名称：

  Lei, Bo; Fallis, Alex G., Journal of the American Chemical Society, 1990, vol. 112, # 11, p. 4609 - 4610

  摘要：

  DOI：

文献信息

• Addition initiated ring closure substituted spiro[4,2]Hepta-1,3-dienes via fulvene intermediates
  作者：Kazimierz Antczak、John F. Kingston、Alex G. Fallis

  DOI：10.1016/s0040-4039(01)81165-5

  日期：1984.1

  The reactivity of the epoxy-fulvene 1 with various nucleophiles has been examined. It is a versatile Intermediate for the preparation of spiro[4.2]hepta-1,3-diene synthons via nucleophilic addition to the C6 position followed by intramolecular cyclization of the substituted cyclopentadiene anion generated in situ.

  已经检查了环氧富烯1与各种亲核试剂的反应性。它是一种通用中间体，可通过亲核加成至C 6位，然后分子内环化原位生成的取代环戊二烯阴离子，来制备螺[4.2]庚-1,3-二烯合成子。
• Regioselective control of allyl anions with cadmium chloride: α γ condensation with aldehydes
  作者：Lei Bo、Alex G Fallis

  DOI：10.1016/s0040-4039(00)85166-7

  日期：1986.1

  A general method for directing the condensation of allyl anions such as with aldehydes preferentially to the γ position of the unsaturated nucleophile is described. The procedure employs cadmium chloride to control the regioselectivity and will facilitate the extended use of vinylogous anions in synthesis.

  描述了将烯丙基阴离子例如与醛的缩合优先引导至不饱和亲核体的γ位置的一般方法。该方法采用氯化镉来控制区域选择性，并有利于乙烯基阴离子在合成中的广泛使用。
• Antczak, Kazimierz; Kingston, John F.; Fallis, Alex G., Canadian Journal of Chemistry, 1984, vol. 62, p. 2451 - 2455
  作者：Antczak, Kazimierz、Kingston, John F.、Fallis, Alex G.

  DOI：——

  日期：——
• Lei, Bo; Fallis, Alex G., Canadian Journal of Chemistry, 1991, vol. 69, # 9, p. 1450 - 1456
  作者：Lei, Bo、Fallis, Alex G.

  DOI：——

  日期：——
• Cycloaddition routes to tricyclo[5.4.01,7.02,9]undecanes: a direct total synthesis of (+)-longifolene via an intramolecular Diels-Alder strategy
  作者：Bo Lei、Alex G. Fallis

  DOI：10.1021/jo00060a039

  日期：1993.4

  The total synthesis of the sesquiterpene (+)-longifolene (1) by an intramolecular Diels-Alder cycloaddition strategy is described. Addition of methyllithium to the epoxyfulvene 13, derived from cyclopentadiene and 3,4-epoxy-2-butanone, led to an exo-tet cyclization of the resulting cyclopentadienyl anion to generate the spiro[2.4]hepta-4,6-diene alcohol 14. Resolution of this material was effected via its menthyl carbonate derivative 15. Oxidation of the (+)-R-alcohol with active MnO2 afforded the cyclopropyl aldehyde 16 which was condensed with the anion derived from methyl 3-methylcrotonate in the presence of cadmium chloride to generate the unsaturated lactone 20 or the unsaturated ester 18. Microwave heating of the silyl triene 19 effected cycloaddition to the adduct 21. Hydrogenolysis of the alcohol 22 afforded the ''sinularene'' skeleton 25. Cyclopropane ring cleavage of the derived ketones 23, 30, and the thiocarbonate 27 was examined but only in the Li/NH3 reduction of 30 was the longifolene skeleton 33 produced as a significant product which unfortunately could not be separated from its isomer 32. Consequently the successful route utilized regiospecific cleavage of the cyclopropane ring in the cyclopentadiene 20 in methanol catalyzed by BF3.Et2O to afford the substituted cyclopentadiene lactone(s) 34 (83%). Cyclization proceeded smoothly, in a sealed tube, in toluene, in a microwave oven to afford the single tetracyclic adduct 39 in 97 % yield. Double bond hydrogenation and reduction of the lactone with LiAlH4 afforded the substituted longifolene skeleton, and the resulting primary alcohol was acetylated selectively to give 40. Free-radical-mediated replacement of the secondary oxygen functions was accomplished via the phenoxythiocarbonate derivative to afford the methoxy acetate 43. Alternatively the reaction sequence could be modified to convert 39 to 41 to 42 and then to 43. Methoxy cleavage (Me3SiI) and a second free-radical reaction gave the acetate 44. Pyrolysis of this acetate (525-degrees-C) provided (+)-longifolene (1).