methyl-norborn-5-ene-2endo-ylmethyl ether | 10471-23-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl-norborn-5-ene-2endo-ylmethyl ether
• 英文别名: Methyl-norborn-5-en-2endo-ylmethyl-aether；(1R,4R,5R)-5-(methoxymethyl)bicyclo[2.2.1]hept-2-ene
• CAS: 10471-23-5；25139-79-1；53848-25-2
• 化学式: C₉H₁₄O
• 分子量: 138.21
• InChiKey: PWRLJYUETHNNFL-VGMNWLOBSA-N

物化性质

• 沸点：
  170.0±9.0 °C(Predicted)
• 密度：
  0.970±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.84
• 重原子数：
  10.0
• 可旋转键数：
  2.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  1.0

反应信息

• 作为产物：
  描述：

  (1R,4R,5R)-5-(phenylselanylmethoxymethyl)bicyclo[2.2.1]hept-2-ene 以5%的产率得到
  参考文献：
  名称：

  Rawal Viresh H., Singh Surendra P., Dufour Claire, Michoud Christophe, J. Org. Chem, 58 (1993) N 27, S 7718-7727

  摘要：

  DOI：

文献信息

• Scope of alkoxymethyl radical cyclizations
  作者：Viresh H. Rawal、Surendra P. Singh、Claire Dufour、Christophe Michoud

  DOI：10.1021/jo00079a016

  日期：1993.12

  We have explored different aspects of the cyclization capability of alkoxymethyl radicals and report here a full account of our investigations. The required radicals were generated from (phenylseleno)methyl ethers (e.g., 6), which were prepared from homoallylic or bis-homoallylic alcohols by a two-step process. The alcohols were alkylated with (iodomethyl)tributylstannane. The stannanes were reacted with n-BuLi, and the resulting alpha-alkoxyanions were trapped with diphenyldiselenide to give the (phenylseleno)methyl ethers, which were stable to chromatography. When treated with tributyltin hydride, in the presence of a radical initiator, these precursors undergo a smooth cyclization to substituted tetrahydrofurans and tetrahydropyrans. Formation of the cyclization product was found to be the primary pathway even at relatively high tin hydride concentration. The diastereoselectivity of this cyclization was comparable to that observed in other radical cyclizations. The cis selectivity in cyclization of 6 increased gradually (up to 11:1) as the reaction temperature was lowered. The cyclization can be used for the synthesis of bicyclic and tricyclic compounds and can be incorporated in systems capable of tandem cyclizations.
• Cyclization of alkoxymethyl radicals
  作者：Viresh H. Rawal、Surendra P. Singh、Claire Dufour、Christophe Michoud

  DOI：10.1021/jo00018a005

  日期：1991.8

  Alkoxymethyl radicals, generated conveniently from phenylseleno precursors, cyclize to afford substituted tetrahydrofurans and tetrahydropyrans in excellent yield and with good stereoselectivity.
• The role of hydrogen migration in the mechanism of alcohol elimination from MH+ ions of ethers upon chemical ionization
  作者：N. Morlender-Vais、A. Mandelbaum

  DOI：10.1002/(sici)1096-9888(199711)32:10<1124::aid-jms570>3.0.co;2-7

  日期：1997.11

  An enhanced elimination of alcohol under isobutane CI conditions, resulting in highly abundant [MH-ROH](+) ions, has been observed in several primary and secondary ethers having a tertiary beta-position (methine), as compared with those with beta-methylene. This elimination exhibits a significant degree of stereospecificity in stereoisomeric 2-methyl-1-methoxycyclohexanes 4 and 1-methoxy-trans-decalins 7, affording more abundant [MH-ROH](+) ions in the cis isomers 4c and 7tc than in their trans counterparts 4t and 7tt. These findings suggest involvement of a 1,2-hydride migration from the beta- to alpha-position in the course of the alcohol elimination from the MH+ ions of the above cis-ethers, resulting in tertiary carbocation structures. The proposed mechanism of alcohol elimination is supported by a considerable deuterium isotope effect detected in beta-deuterium-labeled cis-2-methyl-1-methoxycyclohexane and by a CID study of the structures of [MH-ROH](+) ions obtained from cis- and trans-1,2-dialkoxycyclohexanes. Ring contraction by a Meerwein-type rearrangement has also been observed in the later system. (C) 1997 by John Wiley & Sons, Ltd.No. of Figures: 16 No. of Tables: 1 No. of Refs: 22.
• 40. Aspects of stereochemistry. Part XI. Epoxide formation in the cyclohexene and bicycloheptene series
  作者：H. B. Henbest、B. Nicholls

  DOI：10.1039/jr9590000221

  日期：——