2003
DOI: 10.1021/om030497w
|View full text |Cite
|
Sign up to set email alerts
|

Rate Studies and Mechanism of Ring-Closing Olefin Metathesis Catalyzed by Cationic Ruthenium Allenylidene Arene Complexes

Abstract: The ring-closing metathesis reaction of N,N-diallyltosylamide (2) catalyzed by [(η 6 -pcymene)(PCy 3 )RuCl(dCdCdCPh 2 )]X (X ) OTf (CF 3 SO 3 ) (1), PF 6 , BF 4 , SbF 6 ) and by [(η 6 -pcymene)(PCy 3 )RuCl(dCdCdC(p-Y-C 6 H 4 ) 2 ]OTf (Y ) MeO, Cl, F) complexes has been monitored in situ by 1 H NMR, in benzene-d 6 and in dichloromethane-d 2 , in the temperature range 33-58 °C. The reaction proceeds selectively to form N-tosyl-2,5-dihydropyrrole (3), in the case of complexes [(η 6 -p-cymene)(PCy 3 )RuCl(dCdCdCPh… Show more

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...
1
1
1

Citation Types

1
32
0
1

Year Published

2004
2004
2015
2015

Publication Types

Select...
7
2

Relationship

2
7

Authors

Journals

citations
Cited by 65 publications
(34 citation statements)
references
References 64 publications
(50 reference statements)
1
32
0
1
Order By: Relevance
“…J. Indeed, the [Ru=C=C=CPh 2 (Cl)(PCy 3 )(p-cymene)]X [13] complexes were shown to be active precursors for ROMP on either thermal [14] or acid-promoted [15] transformations into indenylidene-ruthenium derivatives. The indenylidene carbene plays the role of alkene metathesis initiator in these catalyst precursors.…”
Section: Resultsmentioning
confidence: 99%
“…J. Indeed, the [Ru=C=C=CPh 2 (Cl)(PCy 3 )(p-cymene)]X [13] complexes were shown to be active precursors for ROMP on either thermal [14] or acid-promoted [15] transformations into indenylidene-ruthenium derivatives. The indenylidene carbene plays the role of alkene metathesis initiator in these catalyst precursors.…”
Section: Resultsmentioning
confidence: 99%
“…[281] The nature of this catalytic species was established in another observation. It was noticed that protonation of IX a with HBF 4 led to a significant increase in the catalyst activity in the RCM of diallyl tosylamide.…”
Section: Alkene-metathesis Catalysts From Ruthenium Allenylidenesmentioning
confidence: 89%
“…The reactivity of allenylidene ligands attached to different cationic ruthenium fragments such as {[(g 5 -C 9 H 7 )Ru(PPh 3 ) 2 ] + } [5][6][7], {[(g 5 -C 9 H 7 )Ru(CO)(PPh 3 )] + } [5][6][7], {[CpRu-(CO)(P i Pr 3 )] + } [8][9][10][11][12][13][14][15][16][17] or {[(g 6 -arene)RuCl(PR 3 )] + } [18][19][20][21] has been studied by several research groups. Although the reactivity of cationic allenylidene complexes is governed by the electron deficiency of both the C a and C c atoms of the unsaturated chain, its is known that regioselective nucleophilic additions at C c take place when bulky, electron-rich metallic fragments are used, leading to r-alkynyl complexes [2,5].…”
Section: Introductionmentioning
confidence: 99%