Enabling Nucleophilic Substitution Reactions of Activated Alkyl Fluorides through Hydrogen Bonding

被引：83

作者：

Champagne, Pier Alexandre ^{[1
]}

Pomarole, Julien ^{[1
]}

Therien, Marie-Eve ^{[1
]}

Benhassine, Yasmine ^{[1
]}

Beaulieu, Samuel ^{[2
]}

Legault, Claude Y. ^{[2
]}

Paquin, Jean-Francois ^{[1
]}

机构：

[1] Univ Laval, Canada Res Chair Organ & Med Chem, CCVC, PROTEO,Dept Chim, Quebec City, PQ G1V 0A6, Canada

[2] Univ Sherbrooke, Dept Chim, CCVC, Sherbrooke, PQ J1K 2R1, Canada

来源：

ORGANIC LETTERS | 2013年 / 15卷 / 09期

基金：

加拿大创新基金会; 加拿大自然科学与工程研究理事会;

关键词：

C-CL BONDS; CONFORMATIONAL-ANALYSIS; GAS-PHASE; H-H; REACTIVITY; ENERGY; STATE;

D O I：

10.1021/ol400765a

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

It was discovered that the presence of water as a cosolvent enables the reaction of activated alkyl fluorides for bimolecular nucleophilic substitution reactions. DFT calculations show that activation proceeds through stabilization of the transition structure by a stronger F center dot center dot center dot H2O interaction and diminishing C-F bond elongation, and not simple transition state electrostatic stabilization. Overall, the findings put forward a distinct strategy for C-F bond activation through H-bonding.

引用

收藏

页码：2210 / 2213

页数：4

相关论文

共 36 条

[1] C-F Bond Activation in Organic Synthesis [J].

Amii, Hideki ;

Uneyama, Kenji .

CHEMICAL REVIEWS, 2009, 109 (05) :2119-2183

[2] Definition of the hydrogen bond (IUPAC Recommendations 2011) [J].

Arunan, Elangannan ;

Desiraju, Gautam R. ;

Klein, Roger A. ;

Sadlej, Joanna ;

Scheiner, Steve ;

Alkorta, Ibon ;

Clary, David C. ;

Crabtree, Robert H. ;

Dannenberg, Joseph J. ;

Hobza, Pavel ;

Kjaergaard, Henrik G. ;

Legon, Anthony C. ;

Mennucci, Benedetta ;

Nesbitt, David J. .

PURE AND APPLIED CHEMISTRY, 2011, 83 (08) :1637-1641

[3]

Bickelhaupt FM, 1999, J COMPUT CHEM, V20, P114, DOI 10.1002/(SICI)1096-987X(19990115)20:1<114::AID-JCC12>3.0.CO

[4]

2-L

[5] Bond dissociation energies of organic molecules [J].

Blanksby, SJ ;

Ellison, GB .

ACCOUNTS OF CHEMICAL RESEARCH, 2003, 36 (04) :255-263

[6] EFFECT OF CARBONYL + RELATED GROUPS ON REACTIVITY OF HALIDES IN SN2 REACTIONS [J].

BORDWELL, FG ;

BRANNEN, WT .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (21) :4645-&

[7] PROTON RESONANCE SHIFTS OF ACIDS IN LIQUID SULFUR DIOXIDE [J].

BROWNSTEIN, S ;

STILLMAN, AE .

JOURNAL OF PHYSICAL CHEMISTRY, 1959, 63 (12) :2061-2062

[8] Transition-state energy and position along the reaction coordinate in an extended activation strain model [J].

de Jong, G. Theodoor ;

Bickelhaupt, F. Matthias .

CHEMPHYSCHEM, 2007, 8 (08) :1170-1181

[9] Catalytic carbon-halogen bond activation: Trends in reactivity, selectivity, and solvation [J].

de Jong, G. Theodoor ;

Bickelhaupt, F. Matthias .

JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 2007, 3 (02) :514-529

[10] Conformational analysis, stereoelectronic interactions and NMR properties of 2-fluorobicyclo[2.2.1]heptan-7-ols [J].

de Rezende, Fatima M. P. ;

Moreira, Marilua A. ;

Cormanich, Rodrigo A. ;

Freitas, Matheus P. .

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, 2012, 8 :1227-1232

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