Preparation of iodonium ylides: probing the fluorination of 1,3-dicarbonyl compounds with a fluoroiodane

被引:39
作者
Geary, Gemma C. [1 ]
Hope, Eric G. [1 ]
Singh, Kuldip [1 ]
Stuart, Alison M. [1 ]
机构
[1] Univ Leicester, Dept Chem, Leicester LE1 7RH, Leics, England
关键词
INTRAMOLECULAR AMINOFLUORINATION; CATALYZED FLUORINATION; HF; CRYSTAL;
D O I
10.1039/c4ra15733h
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The isolation of iodonium ylide 8, from the reaction of fluoroiodane 1 with ethyl 3-oxo-3phenylpropanoate 5 in the presence of potassium fluoride, provides strong evidence that 1,3-dicarbonyl compounds undergo an addition reaction with fluoroiodane 1 to form an iodonium intermediate which can be deprotonated to generate an iodonium ylide. In the presence of TREAT-HF, however, the iodonium intermediate reacts to form the 2-fluoro-1,3-dicarbonyl product and we propose that fluoroiodane 1 simulates electrophilic fluorination via an addition/substitution mechanism. Further evidence to support this mechanism was obtained by successfully reacting the isolated iodonium ylide 8 with TREAT-HF, hydrochloric acid, acetic acid and p-toluenesulfonic acid to form the 2-fluoro-, 2-chloro-, 2-acetyl-and 2-tosyl-1,3-ketoesters respectively.
引用
收藏
页码:16501 / 16506
页数:6
相关论文
共 27 条
[1]   STRUCTURES OF 2 PHENYLIODONIUM YLIDES [J].
ALCOCK, NW ;
BOZOPOULOS, AP .
ACTA CRYSTALLOGRAPHICA SECTION C-CRYSTAL STRUCTURE COMMUNICATIONS, 1990, 46 :1300-1303
[2]  
BERTHIER G, 1966, CHEM CARBONYL GROUP, P1
[3]   Iodonium ylides for one-step, no-carrier-added radiofluorination of electron rich arenes, exemplified with 4-(([18F] fluorophenoxy)-phenylmethyl) piperidine NET and SERT ligands [J].
Cardinale, Jens ;
Ermert, Johannes ;
Humpert, Sven ;
Coenen, Heinz H. .
RSC ADVANCES, 2014, 4 (33) :17293-17299
[4]   Simplified synthesis of aryliodonium ylides by a one-pot procedure [J].
Cardinale, Jens ;
Ermert, Johannes .
TETRAHEDRON LETTERS, 2013, 54 (16) :2067-2069
[5]   Electrophilic Trifluoromethylation by Use of Hypervalent Iodine Reagents [J].
Charpentier, Julie ;
Frueh, Natalja ;
Togni, Antonio .
CHEMICAL REVIEWS, 2015, 115 (02) :650-682
[6]   Boron Trifluoride Etherate Functioning as a Fluorine Source in an Iodosobenzene-Mediated Intramolecular Aminofluorination of Homoallylic Amines [J].
Cui, Jian ;
Jia, Qun ;
Feng, Ruo-Zhu ;
Liu, Shan-Shan ;
He, Tian ;
Zhang, Chi .
ORGANIC LETTERS, 2014, 16 (05) :1442-1445
[7]   Electrophilic fluorination using a hypervalent iodine reagent derived from fluoride [J].
Geary, Gemma C. ;
Hope, Eric G. ;
Singh, Kuldip ;
Stuart, Alison M. .
CHEMICAL COMMUNICATIONS, 2013, 49 (81) :9263-9265
[8]   Reaction of Iodonium Ylides of 1,3-Dicarbonyl Compounds with HF Reagents [J].
Gondo, Keisuke ;
Kitamura, Tsugio .
MOLECULES, 2012, 17 (06) :6625-6632
[9]   SYNTHESIS OF DIMETHYL 2-PHENYLCYCLOPROPANE-1,1-DICARBOXYLATE USING AN IODONIUM YLIDE DERIVED FROM DIMETHYL MALONATE [J].
Goudreau, Sebastien R. ;
Marcoux, David ;
Charette, Andre B. .
ORGANIC SYNTHESES, 2010, 87 :115-+
[10]   General Method for the Synthesis of Phenyliodonium Ylides from Malonate Esters: Easy Access to 1,1-Cyclopropane Diesters [J].
Goudreau, Sebastien R. ;
Marcoux, David ;
Charette, Andre B. .
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (01) :470-473