Electrophilic Difluoro(phenylthio)methylation: Generation, Stability, and Reactivity of α-Fluorocarbocations

被引：25
作者：
Betterley, Nolan M.
Surawatanawong, Panida
Prabpal, Samran
Kongsaeree, Palangpon
Kuhakarn, Chutima
Pohmakotr, Manat
Reutrakul, Vichai [1 ]
机构：
[1] Mahidol Univ, Fac Sci, Dept Chem, Bangkok 10400, Thailand
来源：
ORGANIC LETTERS | 2013年 / 15卷 / 22期
关键词：
CRAFTS-TYPE CYCLIZATION; FLUORINE; (PHENYLSULFONYL)DIFLUOROMETHYLATION; DIFLUOROALKENES; PHSCF2SIME3; CATION; IONS;
D O I：
10.1021/ol402631t
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Electrophilic difluoro(phenylthio)methylation of allylsilanes has been achieved using bromodifluoro(phenylthio)methane (PhSCF2Br) and silver hexafluoroantimonate (AgSbF6). The structural assignment and observation of alpha-fluorocarbocation were substantiated by NMR and theoretical calculations. Detailed mechanistic and electronic studies have provided a fundamental understanding of the reactivity and stability of the difluoro(phenylthio)methylium cation (PhSCF2+).
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页码：5666 / 5669
页数：4
相关论文
共 36 条
[1]   CRYSTAL-STRUCTURE OF 2,4,4-TRIFLUORO-1,3-DITHIETAN-2-YLIUM HEXAFLUOROARSENATE [J].
ANTEL, J ;
HARMS, K ;
JONES, PG ;
MEWS, R ;
SHELDRICK, GM ;
WATERFELD, A .
CHEMISCHE BERICHTE-RECUEIL, 1985, 118 (12) :5006-5008
[2]   Predicting 13C NMR spectra by DFT calculations [J].
Bagno, A ;
Rastrelli, F ;
Saielli, G .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (46) :9964-9973
[3]   Fluoride-Catalyzed Addition of PhSCF2SiMe3 to N-Substituted Cyclic Imides Followed by Radical Cyclization: General Synthetic Strategy of gem-Difluoromethylenated 1-Azabicyclic Compounds [J].
Bootwicha, Teerawut ;
Panichakul, Duanghathai ;
Kuhakarn, Chutima ;
Prabpai, Samran ;
Kongsaeree, Palangpon ;
Tuchinda, Patoomratana ;
Reutrakul, Vichai ;
Pohmakotr, Manat .
JOURNAL OF ORGANIC CHEMISTRY, 2009, 74 (10) :3798-3805
[4]   Relative abilities of fluorine and chlorine to stabilize carbenium ions:: Crystal structures of two fluoro-substituted carbocations and of As2F11- [J].
Christe, KO ;
Zhang, XZ ;
Bau, R ;
Hegge, J ;
Olah, GA ;
Prakash, GKS ;
Sheehy, JA .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (03) :481-487
[5]   Fluoroanions and cations in the HF-SbF5 superacid system.: A 19F and 1H NMR study [J].
Culmann, JC ;
Fauconet, M ;
Jost, R ;
Sommer, J .
NEW JOURNAL OF CHEMISTRY, 1999, 23 (08) :863-867
[6]  
de Nooy A. E., 2000, SYNTHESIS-STUTTGART, V1996, P1153
[7]   Isolating fluorinated carbocations [J].
Douvris, Christos ;
Stoyanov, Evgenii S. ;
Tham, Fook S. ;
Reed, Christopher A. .
CHEMICAL COMMUNICATIONS, 2007, (11) :1145-1147
[8]   Domino Friedel-Crafts-Type Cyclizations of Difluoroalkenes Promoted by the α-Cation-Stabilizing Effect of Fluorine: An Efficient Method for Synthesizing Angular PAHs [J].
Fuchibe, Kohei ;
Jyono, Hideharu ;
Fujiwara, Masaki ;
Kudo, Takao ;
Yokota, Misaki ;
Ichikawa, Junji .
CHEMISTRY-A EUROPEAN JOURNAL, 2011, 17 (43) :12175-12185
[9]   β-arylthio-α-chloroalkyl ethers -: Novel 1,1-bis-electrophiles for geminal alkylation [J].
Gromov, AV ;
Smit, WA .
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2006, 2006 (05) :1317-1322
[10]  
He Z., 2012, ANGEW CHEM, V124, P11713
1234