Probing the mechanism of the petasis olefination reaction by atmospheric pressure chemical ionization mass and tandem mass spectrometry

被引:54
作者
Meurer, EC [1 ]
Santos, LS [1 ]
Pilli, RA [1 ]
Eberlin, MN [1 ]
机构
[1] Univ Estadual Campinas, Inst Chem, BR-13083970 Campinas, SP, Brazil
关键词
D O I
10.1021/ol027439b
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
graphic Atmospheric pressure chemical ionization mass (APCI-MS) and tandem mass spectrometry (APCI-MS/MS) is used to probe the mechanism of the Petasis olefination reaction. Oxatitanacycle intermediates 4 were transferred from solution to the gas phase, detected as 4H(+) by APCI-MS with characteristic Ti-isotopic patterns, and structurally characterized by APCI-MS/MS. Detection of 4H(+), which upon collision activation dissociates to both 3H(+) and Cp2TiOH+, fully supports the Hughes mechanism as depicted above.
引用
收藏
页码:1391 / 1394
页数:4
相关论文
共 50 条
[1]   AUTOMATED THERMAL-DEGRADATION STUDIES ON SOLID SIGMA-ORGANOTRANSITION METAL-COMPLEXES - DIMETHYL-TITANOCENE, DIMETHYL-ZIRCONOCENE AND DIMETHYL-HAFNOCENE [J].
ALT, HG ;
DISANZO, FP ;
RAUSCH, MD ;
UDEN, PC .
JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1976, 107 (02) :257-263
[2]   MECHANISM OF TITANOCENE METALLACYCLOBUTANE CLEAVAGE AND THE NATURE OF THE REACTIVE INTERMEDIATE [J].
ANSLYN, EV ;
GRUBBS, RH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (16) :4880-4890
[3]   SELECTIVE INTERMOLECULAR CARBON-HYDROGEN BOND ACTIVATION BY SYNTHETIC METAL-COMPLEXES IN HOMOGENEOUS SOLUTION [J].
ARNDTSEN, BA ;
BERGMAN, RG ;
MOBLEY, TA ;
PETERSON, TH .
ACCOUNTS OF CHEMICAL RESEARCH, 1995, 28 (03) :154-162
[4]   Selectivities in hydrocarbon activation: Kinetic and thermodynamic investigations of reversible 1,2-RH-elimination from (silox)(2)((Bu3SiNH)-Bu-t)TiR (silox = (Bu3SiO)-Bu-t) [J].
Bennett, JL ;
Wolczanski, PT .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1997, 119 (44) :10696-10719
[5]   CP2TICH2 COMPLEXES IN SYNTHETIC APPLICATIONS [J].
BROWNWENSLEY, KA ;
BUCHWALD, SL ;
CANNIZZO, L ;
CLAWSON, L ;
HO, S ;
MEINHARDT, D ;
STILLE, JR ;
STRAUS, D ;
GRUBBS, RH .
PURE AND APPLIED CHEMISTRY, 1983, 55 (11) :1733-1744
[6]  
Cole R.B., 1997, Electrospray Ionization Mass Spectrometry
[7]   Electrospray mass spectrometry applied inorganic and organometallic chemistry [J].
Colton, R ;
DAgostino, A ;
Traeger, JC .
MASS SPECTROMETRY REVIEWS, 1995, 14 (02) :79-106
[8]   Chiroselective self-directed octamerization of serine: Implications for homochirogenesis [J].
Cooks, RG ;
Zhang, DX ;
Koch, KJ ;
Gozzo, FC ;
Eberlin, MN .
ANALYTICAL CHEMISTRY, 2001, 73 (15) :3646-3655
[9]   AN INVESTIGATION OF THE ZIEGLER CATALYSTS OBTAINED BY TREATING TITANIUM TETRACHLORIDE WITH ALUMINIUM ALKYLS [J].
COOPER, ML ;
ROSE, JB .
JOURNAL OF THE CHEMICAL SOCIETY, 1959, (FEB) :795-802
[10]   EVIDENCE FOR REVERSIBLE ALPHA-ELIMINATION OF HYDROGEN FROM A TUNGSTEN-METHYL COMPOUND GIVING A TUNGSTEN-METHYLENE-HYDRIDE DERIVATIVE [J].
COOPER, NJ ;
GREEN, MLH .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1974, (18) :761-762