trans-(±)-2-(iodomethyl)-3-methyltetrahydrofuran | 109065-89-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: trans-(±)-2-(iodomethyl)-3-methyltetrahydrofuran
• 英文别名: (2R,3R)-2-(iodomethyl)-3-methyloxolane
• CAS: 109065-89-6
• 化学式: C₆H₁₁IO
• 分子量: 226.057
• InChiKey: VUOFVPICSOHCMC-RITPCOANSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.85
• 重原子数：
  8.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  3-甲基-4-戊醇 生成 trans-(±)-2-(iodomethyl)-3-methyltetrahydrofuran
  参考文献：
  名称：

  REITZ, ALLEN B.;NORTEY, SAMUEL O.;MARYANOFF, BRUCE E.;LIOTTA, DENNIS;MONA+, J. ORG. CHEM., 52,(1987) N 19, 4191-4202

  摘要：

  DOI：

文献信息

• Halocyclization of Unsaturated Alcohols and Carboxylic Acids Using Bis(<i>sym</i>-collidine)iodine(I) Perchlorate
  作者：Robert D. Evans、Joseph W. Magee、J. Herman Schauble

  DOI：10.1055/s-1988-27731

  日期：——

  Reaction of I(collidine)+ 2 ClO- 4 with unsaturated alcohols and carboxylic acids in dichloromethane at ambient temperature has afforded three- to seven-membered-ring iodoethers and four- to seven-membered-ring iodolactones, respectively, in moderate yields and generally with high regioselectivity. The reaction is of particular utility for synthesis of 2-(1-iodoalkyl)oxiranes and -oxetanes.

  I（吡啶啉）与2ClO₄在室温下与不饱和醇和羧酸在二氯甲烷中反应，得到了三至七元环的碘醚和四至七元环的碘内酯，产率适中且通常具有高区域选择性。该反应特别适用于合成2-(1-碘烷基)环氧烷和环丁烷。
• Stereoselectivity of electrophile-promoted cyclizations of .gamma.-hydroxyalkenes. An investigation of carbohydrate-derived and model substrates
  作者：Allen B. Reitz、Samuel O. Nortey、Bruce E. Maryanoff、Dennis Liotta、Robert Monahan

  DOI：10.1021/jo00228a009

  日期：1987.9
• Molecular Basis for the Enantio- and Diastereoselectivity of<i>Burkholderia cepacia</i>Lipase toward γ-Butyrolactone Primary Alcohols
  作者：Heesung Eum、Romas J. Kazlauskas、Hyun-Joon Ha

  DOI：10.1002/adsc.201400510

  日期：2014.11.24

  AbstractBurkholderia cepacia lipase (BCL) shows high enantioselectivity toward chiral primary alcohols, but this enantioselectivity is often unpredictable, especially for substrates that contain an oxygen at the stereocenter. For example, BCL resolves β‐substituted‐γ‐acetyloxymethyl‐γ‐butyrolactones (acetates of a chiral primary alcohol) by hydrolysis of the acetate, but the enantioselectivity varies with the nature and orientation of the β‐alkyl substituent. BCL favors the (R)‐primary alcohol when the β‐alkyl substituent is hydrogen (E=30) or trans methyl (E=38), but the (S)‐primary alcohol when it is cis methyl (E=145). To rationalize this unusual selectivity, we used a combination of experiments to show the importance of polar interactions and modeling to reveal differences in orientations of the enantiomers. Removal of either the lactone carbonyl in the substrate or the polar side chains in the enzyme by using a related enzyme without these side chains decreased the enantioselectivity at least four‐fold. Modeling revealed that the slow enantiomers do not bind by exchanging the location of two substituents relative to the fast enantiomer. Instead, three substituents remain in the same region, but the fourth substituent, hydrogen, inverts to a new location, like an umbrella in a strong wind. In this orientation the favored stereoisomers have similar shapes, thus accounting for the unusual stereoselectivity. The ratio of catalytically productive orientations for the fast vs. slow enantiomers in a molecular dynamic simulation correlated (R2=0.82) with the degree of enantioselectivity including the case where the enantioselectivity reversed. Weighting this ratio by the ratio of H‐bonds in the polar interaction to account for different binding strengths improved the correlation with the measured enantioselectivity to R2=0.97. The modeling identifies key interactions responsible for high enantioselectivity in this class of substrates.magnified image