(1R*,2S*,5R*)-2-methylbicyclo<3.3.0>octan-1-ol | 101327-91-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,2S*,5R*)-2-methylbicyclo<3.3.0>octan-1-ol
• 英文别名: cis-2-endo-methylbicyclo<3.3.0>octan-1-ol；2-methylbicyclo<3.3.0>octan-1-ol；(3R,3aS,6aS)-3-methyl-2,3,4,5,6,6a-hexahydro-1H-pentalen-3a-ol
• CAS: 101327-91-7
• 化学式: C₉H₁₆O
• 分子量: 140.225
• InChiKey: FPKJNAMFKLJIRN-VGMNWLOBSA-N

物化性质

• 沸点：
  209.3±8.0 °C(Predicted)
• 密度：
  1.041±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  4-戊烯酸乙酯 在 samarium diiodide 、 三哌啶氧膦 、 sodium iodide 、 叔丁醇 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 丙酮 为溶剂， 反应 17.25h， 生成 (1R*,2S*,5R*)-2-methylbicyclo<3.3.0>octan-1-ol
  参考文献：
  名称：

  Intramolecular nucleophilic acyl substitution reactions of halo-substituted esters and lactones. New applications of organosamarium reagents

  摘要：

  Intramolecular nucleophilic acyl substitution reactions involving a broad range of halo substituted carboxylic acid derivatives have been accomplished in excellent yield employing samarium(II) iodide as the reductive coupling agent. Although particular substrates cyclized most effectively in THF in the presence of tripiperidinophosphine oxide, carboxylic acid esters, the focus of this report, cyclize equally well without such an additive in the presence of a catalytic quantity of iron(III) complexes. Thus a comprehensive series of halo substituted esters were cyclized in excellent yield to the corresponding 4-, 5-, and 6-membered carbocycles. The reaction is extremely mild and selective as demonstrated by experiments wherein alkyl chlorides, acetals, and olefins remain completely intact under the reaction conditions. In addition to introducing a convenient procedure for preparing stereodefined spirocyclic systems, a new ring expansion sequence has been developed that appears extremely general for the preparation of various ring systems.

  DOI：

  10.1021/jo00077a053

文献信息

• Cyclopentane synthesis and annulation II: Radical cyclizations of oxathiolanones
  作者：Veejendra Yadav、Alex G. Fallis

  DOI：10.1016/s0040-4039(00)99222-0

  日期：1989.1

  A general procedure for the synthesis of diverse cyclopentanols via free-radical cyclization of 1,3-oxathiolan-5-ones is described. This permits the rapid assembly, by intramolecular annulation, of various ring systems for use in total synthesis.

  描述了通过1，3-氧杂噻喃-5-酮的自由基环合反应合成各种环戊醇的一般程序。这允许通过分子内环化快速组装各种环系统以用于全合成。
• Radical cyclizations of bromo acylsilanes and intramolecular trapping of the rearranged α-silyloxy radicals
  作者：Yeun-Min Tsai、Kuo-Hsiang Tang、Weir-Torn Jiaang

  DOI：10.1016/s0040-4039(00)91780-5

  日期：1993.2

  Radical 1,5-exo cyclizations of acylsilanes involving secondary radicals are quite effective. In contrast, 1,6-exo cyclizations are more sensitive toward steric effect. Tandem radical cyclization process can be designed.
• Yadav, Veejendra; Fallis, Alex G., Canadian Journal of Chemistry, 1991, vol. 69, # 5, p. 779 - 789
  作者：Yadav, Veejendra、Fallis, Alex G.

  DOI：——

  日期：——
• Samarium(II) iodide-induced reductive cyclization of unactivated olefinic ketones. Sequential radical cyclization/intermolecular nucleophilic addition and substitution reactions
  作者：Gary A. Molander、Jeffrey A. McKie

  DOI：10.1021/jo00037a033

  日期：1992.5

  Samarium(II) iodide in the presence of HMPA effectively promotes the intramolecular coupling of unactivated olefinic ketones by a reductive ketyl-olefin radical-cyclization process. The reaction is quite general for the formation of 5- and 6-membered carbocycles and even provides modest yields in less facile cyclization processes as evidenced by the generation of methylcyclooctanol via an 8-endo cyclization. Sequential radical cyclization-intermolecular nucleophilic addition/substitution processes set the SmI2 reaction apart from its radical-chain, photochemical, and electrochemical counterparts. In addition to delineating the synthetic potential of this reaction, the role played by HMPA in enhancing SmI2 reactivity has been further refined, and a model correlating the high diastereoselectivity and product distribution in SmI2-promoted reductive coupling processes with HMPA concentration has been established.