On the synergism between H2O and a tetrahydropyran template in the regioselective cyclization of an epoxy alcohol

被引：0
|
作者：
Byers, Jeffery A. [1 ]
Jamison, Timothy F. [1 ]
机构：
[1] Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, United States
来源：
Journal of the American Chemical Society | 2009年 / 131卷 / 18期
关键词：
A regioselective epoxy alcohol cyclization promoted by the combination of neutral water and a tetrahydropyran template was investigated through a series of mechanistic experiments carried out on an epoxy alcohol containing a tetrahydropyran ring (1a) and its carbocyclic congener (1b). In contrast to 1a; cyclizations of 1b were unselective and displayed significantly faster reaction rates suggesting that the tetrahydropyran oxygen in 1a is requisite for regioselective cyclization. Reactions for both substrates were shown to occur in solution and under kinetic control without significant influence from hydrophobic effects. Kinetic measurements carried out in water/dimethyl sulfoxide mixtures suggest that 1b reacts exclusively through an unselective pathway requiring one water molecule more than what is required to solvate the epoxy alcohol. Similar experiments for 1a suggest a competition between an unselective and a selective pathway requiring one and two water molecules in excess of those required to solvate 1a; respectively. The selective pathway observed for 1a but not in 1b is rationalized by electronic and conformational differences between the two compounds. Copyright © 2009 American Chemical Society;
D O I：
暂无
中图分类号：
学科分类号：
摘要：
Journal article (JA)
引用
收藏
页码：6383 / 6385
相关论文
共 50 条
  • [1] On the Synergism Between H2O and a Tetrahydropyran Template in the Regioselective Cyclization of an Epoxy Alcohol
    Byers, Jeffery A.
    Jamison, Timothy F.
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (18) : 6383 - +
  • [2] Equilibrium conditions hydrate dissociation of CO2 + cyclopentene or tetrahydropyran + H2O
    Song, Jia
    Sun, Zhi-Gao
    Li, Rong
    Dai, Meng-Ling
    JOURNAL OF CHEMICAL THERMODYNAMICS, 2021, 163
  • [3] REGIOSELECTIVE OPENING OF EPOXIDE RING WITH PRIMARY AMINES IN H2O MEDIUM
    Abdullayev, Yusif A.
    Abbasov, Vaqif M.
    Talybov, Avtandil H.
    Salmanov, Javanshir S.
    Yunusova, Aytan S.
    Valiyev, Isa A.
    Baybekov, Shamkhal R.
    Akhmadova, Sabina Z.
    Rzayeva, Nigar Sh.
    PROCESSES OF PETROCHEMISTRY AND OIL REFINING, 2016, 17 (02): : 75 - 80
  • [4] The non-covalently bound SO•••H2O system, including an interpretation of the differences between SO•••H2O and O2•••H2O
    Misiewicz, Jonathon P.
    Noonan, Julia A.
    Turney, Justin M.
    Schaefer, Henry F., III
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2018, 20 (45) : 28840 - 28847
  • [5] The water dimer reaction OH + (H2O)2 → (H2O)-OH + H2O
    Gao, Aifang
    Li, Guoliang
    Peng, Bin
    Xie, Yaoming
    Schaefer, Henry F., III
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2017, 19 (28) : 18279 - 18287
  • [6] TRANSFERABILITY OF ELECTRON PAIRS BETWEEN H2O AND H2O2
    LEVY, M
    STEVENS, WJ
    SHULL, H
    HAGSTROM, S
    JOURNAL OF CHEMICAL PHYSICS, 1974, 61 (05): : 1844 - 1856
  • [7] SCF-CI STUDIES OF CORRELATION EFFECTS ON HYDROGEN-BONDING AND ION HYDRATION - SYSTEMS - H2O,H+ . H2O, LI+ . H2O, F- . H2O, AND H2O . H2O
    DIERCKSEN, GHF
    KRAEMER, WP
    ROOS, BO
    THEORETICA CHIMICA ACTA, 1975, 36 (04): : 249 - 274
  • [8] PROTON MAGNETIC SHIELDING IN H2O AND (H2O)2
    JASZUNSKI, M
    SADLEJ, AJ
    THEORETICA CHIMICA ACTA, 1973, 30 (03): : 257 - 265
  • [9] Theoretical study of mixed hydrogen-bonded complexes:: H2O•••HCN•••H2O and H2O•••HCN•••HCN•••H2O
    Rivelino, R
    Canuto, S
    JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (50): : 11260 - 11265
  • [10] FRACTIONATION OF OXYGEN ISOTOPES BETWEEN NO AND H2O
    JORDAN, S
    BONNER, FT
    JOURNAL OF CHEMICAL PHYSICS, 1971, 54 (11): : 4963 - &
12345