Intramolecular microsolvation of SN2 transition states

被引:42
|
作者
Craig, SL [1 ]
Brauman, JI [1 ]
机构
[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA
关键词
D O I
10.1021/ja983010x
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Introduction of an omega-substituent (CN, Cl, or OH) onto a primary n-alkyl chloride significantly enhances the rate of S(N)2 chloride exchange in the gas phase. Trends in reactivity suggest that the rate acceleration depends primarily on through-space solvation of the transition state, especially charge-dipole interactions. The potential energy surfaces and dynamics of these reactions are discussed.
引用
收藏
页码:6690 / 6699
页数:10
相关论文
共 50 条
  • [31] Improved stereoselectivity in intramolecular SN2′ cyclization through use of mechanistic principles
    Seo, Woo Duck
    Curtis-Long, Marcus J.
    Jeong, Seong Hun
    Jun, Tae Hong
    Yang, Min Suk
    Park, Ki Hun
    SYNTHESIS-STUTTGART, 2007, (02): : 209 - 214
  • [32] RING FORMATION THROUGH INTRAMOLECULAR SN2' DISPLACEMENT OF AN ALLYLIC METHOXY SUBSTITUENT
    HARMS, AE
    TAYLOR, SK
    STILLE, JR
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1993, 205 : 332 - ORGN
  • [33] 气相氯交换的SN2(C)、SN2(N)、SN2(Si)和SN2(P)反应的理论研究
    丁艳丽
    黑龙江大学自然科学学报, 2013, 30 (06) : 773 - 778
  • [34] The importance of the composite mechanisms with two transition states in the F-+ NH2I SN2 reaction
    Li, Yan
    Li, Yongfang
    Wang, Dunyou
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2020, 22 (23) : 12929 - 12938
  • [35] THE SN2' REACTION .3. STRUCTURE AND SN2' REACTIONS OF THE HALOCODIDES
    STORK, G
    CLARKE, FH
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1956, 78 (18) : 4619 - 4624
  • [36] Chemoselective tandem SN2′/SN2′′/inter- or intramolecular Diels-Alder reaction of γ-vinyl MBH carbonates with phenols and o-hydroxychalcones
    Liu, Wei
    Zhang, Le
    Liu, Ye
    Fan, Shi-Lu
    Dai, Jian-Jun
    Tao, Wei
    Zhu, Hui-Xia
    Xiao, Hua
    CHEMICAL COMMUNICATIONS, 2022, 58 (70) : 9794 - 9797
  • [37] Intramolecular SN2 reaction α- to a trifluoromethyl group:: preparation of 1-cyano-2-trifluoromethylcyclopropane
    Katagiri, T
    Irie, M
    Uneyama, K
    TETRAHEDRON-ASYMMETRY, 1999, 10 (13) : 2583 - 2589
  • [38] Intramolecular nucleophilic SN2 substitution at the tetrahedral carbon atom:: an ab initio study
    Minyaev, RM
    Minkin, VI
    RUSSIAN CHEMICAL BULLETIN, 1999, 48 (07) : 1234 - 1245
  • [39] IS CHARGE DEVELOPMENT A MEASURE OF SN2 TRANSITION-STATE STRUCTURE
    PROSS, A
    SHAIK, SS
    TETRAHEDRON LETTERS, 1982, 23 (51) : 5467 - 5470
  • [40] TRANSITION-STATE ELECTRONIC-STRUCTURES IN SN2 REACTIONS
    SHI, Z
    BOYD, RJ
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (05) : 1575 - 1579