| 133549-41-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• CAS: 133549-41-4
• 化学式: C₇H₁₃LiO₂
• 分子量: 136.12
• InChiKey: NPULLZMBCJHFAN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.98
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  在 盐酸 、 copper(I) bromide dimethylsulfide complex 、 氯化铵 作用下， 以 四氢呋喃 为溶剂， 反应 2.0h， 生成 3-(4-oxopentyl)cyclohexanone
  参考文献：
  名称：

  Masked lithium bishomoenolates: useful intermediates in organic synthesis

  摘要：

  The lithiation of the chloro ketals 9 with lithium naphthalenide at -78-degrees-C led to the corresponding masked lithium bishomoenolates 4, which are stable species under these conditions and react with different electrophilic reagents (H2O, D2O, i-PrCHO, PhCHO, MeCOEt, (activated CH2)4CO, (activated CH2)5CO, (activated CH2)7CO, PhCOMe, c-C3H5COPh, PhCN, HCONMe2, PrCO activated N(CH2)4, PhCO activated N(CH2)4, PhCOCl, EtOCOCl, PhCHNPh, and (PhCH2S)2) to give, after hydrolysis with water, the corresponding bifunctionalized compounds 10a-22a, 10b-22b, and 10c-15c. When alkyl halides were used as electrophiles the reaction failed. In the presence of a catalytic amount of the complex CuBr.Me2S, the same reaction with alpha,beta-unsaturated ketones (methyl vinyl ketone or 2-cyclohexanone) yielded the expected products of a 1,4-addition 25a-c and 26b. The deprotection of the masked carbonyl group was easily done by treatment with 2 N hydrochloric acid in THF, so as examples, compounds 27a-29a, 30b, 31b, 32c, and 33c were isolated. The transformation of hemiacetals of the type 27a into substituted tetrahydropyrans was carried out by means of compounds of the type R3SiNu (Nu = H, allyl, CN) in the presence of BF3, so products 34a-41a, 42b, and 43b were prepared. Finally, the in situ oxidation of the deprotected products of the type 27a-arising from the reaction of bishomoenolate 4a with carbonyl compounds-with Jones reagent (for ketones derivatives) or PCC (for aldehydes derivatives) led to the corresponding delta-lactones 44-57.

  DOI：

  10.1021/jo00012a012
• 作为产物：
  描述：

  5-氯-2-戊酮 在 联苯 lithium 作用下， 以 四氢呋喃 为溶剂， 生成
  参考文献：
  名称：

  ROMPgel-supported biphenyl and naphthalene: reagents for lithiation reactions with minimal purification

  摘要：

  The synthesis of ring opening metathesis, polymer (ROMPgel) supported naphthalene and biphenyl reagents was carried out. These reagents were utilized for catalytic lithiation reactions of aryl and alkyl chlorides and for the reductive deprotection of benzyl and allyl ethers. (C) 2002 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)02317-6

文献信息

• Masked lithium bishomoenolates: useful intermediates in organic synthesis
  作者：Diego J. Ramon、Miguel Yus

  DOI：10.1021/jo00012a012

  日期：1991.6

  The lithiation of the chloro ketals 9 with lithium naphthalenide at -78-degrees-C led to the corresponding masked lithium bishomoenolates 4, which are stable species under these conditions and react with different electrophilic reagents (H2O, D2O, i-PrCHO, PhCHO, MeCOEt, (activated CH2)4CO, (activated CH2)5CO, (activated CH2)7CO, PhCOMe, c-C3H5COPh, PhCN, HCONMe2, PrCO activated N(CH2)4, PhCO activated N(CH2)4, PhCOCl, EtOCOCl, PhCHNPh, and (PhCH2S)2) to give, after hydrolysis with water, the corresponding bifunctionalized compounds 10a-22a, 10b-22b, and 10c-15c. When alkyl halides were used as electrophiles the reaction failed. In the presence of a catalytic amount of the complex CuBr.Me2S, the same reaction with alpha,beta-unsaturated ketones (methyl vinyl ketone or 2-cyclohexanone) yielded the expected products of a 1,4-addition 25a-c and 26b. The deprotection of the masked carbonyl group was easily done by treatment with 2 N hydrochloric acid in THF, so as examples, compounds 27a-29a, 30b, 31b, 32c, and 33c were isolated. The transformation of hemiacetals of the type 27a into substituted tetrahydropyrans was carried out by means of compounds of the type R3SiNu (Nu = H, allyl, CN) in the presence of BF3, so products 34a-41a, 42b, and 43b were prepared. Finally, the in situ oxidation of the deprotected products of the type 27a-arising from the reaction of bishomoenolate 4a with carbonyl compounds-with Jones reagent (for ketones derivatives) or PCC (for aldehydes derivatives) led to the corresponding delta-lactones 44-57.
• ROMPgel-supported biphenyl and naphthalene: reagents for lithiation reactions with minimal purification
  作者：Thomas Arnauld、Anthony G.M. Barrett、Brian T. Hopkins

  DOI：10.1016/s0040-4039(01)02317-6

  日期：2002.2

  The synthesis of ring opening metathesis, polymer (ROMPgel) supported naphthalene and biphenyl reagents was carried out. These reagents were utilized for catalytic lithiation reactions of aryl and alkyl chlorides and for the reductive deprotection of benzyl and allyl ethers. (C) 2002 Elsevier Science Ltd. All rights reserved.