Radical reactions in the coordination sphere I. Addition of carbon tetrachloride and chloroform to 1-olefins catalyzed by ruthenium(II) complexes.

Matsumoto, Hideyuki; Nakano, Taichi; Nagai, Yoichiro

doi:10.1016/s0040-4039(01)87410-4

Cited by 125 publications

(76 citation statements)

References 19 publications

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“…Solvent and unreacted MMA were dried using a rotary evaporator. The yield of the product was calculated based on integration of 1 H NMR resonances at 6.01 ppm (-CCl2H from the product) and 1.84 ppm (-CH3 from the product and byproducts). All of the ATRA reactions in this paper were performed following this general procedure using the same molar ratio of Decomposition study of ruthenium benzylidene complexes.…”

Section: Methodsmentioning

confidence: 99%

“…The NMR tube was capped with a septum, removed from the glovebox, and heated to 65 °C. 1 H NMR spectra were collected at predetermined time points, and the integral of the benzylidene resonance (16-20 ppm, 1 H) was plotted as a function of time.…”

Section: Methodsmentioning

confidence: 99%

“…Since the first report of ruthenium-based catalysts in atom transfer radical addition (ATRA, also called Kharasch addition) 1 and atom transfer radical polymerization (ATRP), 2 this area of research has attracted widespread interest. [3][4][5][6][7][8][9][10][11][12][13][14] Well-defined ruthenium benzylidene complexes, commonly used as olefin metathesis catalysts, have also been reported to catalyze ATRA and ATRP.…”

Section: Introductionmentioning

confidence: 99%

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In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

et al. 2016

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Ruthenium benzylidene complexes are well known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by 1 H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, pre-activated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes is the active catalyst in ATR reactions. Based on data from 1 H, 13 C, and 31 P NMR spectroscopy, and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

et al. 2016

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“…The first active ruthenium catalyst described for such processes was [RuCl2(PPh3)3] [23] and ever since many others have been developed. This issue has been previously reviewed by Demonceau and Noels.…”

Section: Ruthenium-based Catalystmentioning

confidence: 99%

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

2011

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Transition‐metal‐catalyzed atom transfer radical reactions of halogenated compounds with olefins constitute a versatile tool in organic synthesis within the area of C–C bond forming transformations. The inter‐ or intramolecular versions, atom transfer radical addition (ATRA) or cyclization (ATRC), respectively, lead to the atom‐economic, useful synthesis of compounds that can be further functionalized. This contribution summarizes the recent developments in this area in terms of catalyst design as well as the applicability of this methodology in sequential, domino, or tandem reactions.

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“…SUA can be controlled if the resultant dormant species is less reactive for radical generation than that of the starting dormant species, leading to suppression of chain-growth oligomerization. Indeed, some examples of atom transfer radical addition or the Kharasch addition reaction, 60 which is SUA on the basis of ATRP, rely on the mechanism of using non-conjugated olefins, producing less reactive dormant species in conjunction with more reactive halide compounds to produce conjugated radical species. To repeat the SUA process towards sequence control, some additional design or mechanism is required.…”

Section: Sequence-defined Copolymer Via Iterative Suamentioning

confidence: 99%

Sequence-controlled polymers via reversible-deactivation radical polymerization

Ouchi

Sawamoto

2017

Polym J

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The development of reversible-deactivation radical polymerization (RDRP) has made a great contribution not only in controlling the molecular weight and terminal structures but also in the precise synthesis of copolymers. An additional design for controlled propagation via RDRP could lead to control of the order of repeating units, that is, the 'sequence control', which has been recognized as the ultimate control of precision polymerizations. In this review article, some concepts and methodologies are summarized for synthesizing sequence-controlled polymers based on RDRP.

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Radical reactions in the coordination sphere I. Addition of carbon tetrachloride and chloroform to 1-olefins catalyzed by ruthenium(II) complexes.

Cited by 125 publications

References 19 publications

In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

Sequence-controlled polymers via reversible-deactivation radical polymerization

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