Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings

Gilbert, Bruce C.; Kalz, Wilhelm; Lindsay, Christopher D.; McGrail, P.T.; Parsons, Andrew F.; Whittaker, D.

doi:10.1039/b000835o

Cited by 70 publications

(46 citation statements)

References 28 publications

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“…The combined organic layers were washed with water (100 mL) and brine (2 × 100 mL), dried over Na 2 SO 4 , filtered, and concentrated in vacuo. Purification by silica gel column chromatography using a gradient solvent system (20:1 hexane:EtOAc → 6:1 hexane:EtOAc) as the eluent provided a mixture of S1 and S2 in 4.9:1 molar ratio, as determined by 1 H NMR (4.26 g, 55% yield). For simplicity, only analytical data for S1 are reported.…”

Section: 79%mentioning

confidence: 99%

“…The reaction was allowed to cool to room temperature. A small aliquot was taken, concentrated in vacuo, and analyzed by 1 S-15 not proceeded to >95% conversion, an additional portion of tert-butylamine commensurate with the amount of starting material remaining was added, and the reaction was heated for an additional 2-4 h. Upon completion, the reaction mixture was allowed to cool to room temperature, and the solvent was removed in vacuo. The crude imine product (S11) was obtained as a yellow oil and was used in the subsequent step without further purification.…”

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Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

et al. 2015

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A series of second-generation ruthenium olefin metathesis catalysts was investigated using a combination of reaction kinetics, X-ray crystallography, NMR spectroscopy, and DFT calculations in order to determine the relationship between the structure of the chelating oalkoxybenzylidene and the observed initiation rate. Included in this series were previously reported catalysts containing a variety of benzylidene modifications as well as four new catalysts containing cyclopropoxy, neopentyloxy, 1-adamantyloxy, and 2-adamantyloxy groups. The initiation rates of this series of catalysts were determined using a UV/vis assay. All four new catalysts were observed to be faster-initiating than the corresponding isopropoxy control, and the 2-adamantyloxy catalyst was found to be among the fastest-initiating Hoveyda-type catalysts reported to date. Analysis of the X-ray crystal structures and computed energy-minimized structures of these catalysts revealed no correlation between the Ru−O bond length and Ru−O bond strength. On the other hand, the initiation rate was found to correlate strongly with the computed Ru−O bond strength. This latter finding enables both the rationalization and prediction of catalyst initiation through the calculation of a single thermodynamic parameter in which no assumptions about the mechanism of the initiation step are made.

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Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

et al. 2015

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“…Indeed, while UV leads to CO loss to Mn 2 (CO) 9 and Mn(CO) 5 Mn(CO) 5 • easily abstracts hydrides and halide from e.g. Bu 3 SnH (97), and respectively from RX halides with moderate to high BDEs (< 310 kJ/mol) (98) such as CCl 4 (99), I 2 (85), polyhalides (84), allyl and benzyl halides (84,85), and even CH 3 I (100) and other inactivated alkyl iodides. Remarkably, unlike other radical abstractors, Mn(CO) 5 • reacts faster with primary rather than secondary or tertiary halides, due to the sterics of the CO ligands (84).…”

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confidence: 99%

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn₂(CO)₁₀and Visible Light

Simpson

Adebolu

Kim

et al. 2015

ACS Symposium Series

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“…further utilized in metallate alkylation or acylation reactions. 7 -9 Recently, photochemically generated radicals from Mn 2 (CO) 10 in conjunction with alkyl halides have been successfully used in radical-based reactions such as cyclization (vi) 10,11 , coupling (vii) 12 , intermolecular addition (viii) 13 and polymerization (Scheme 2).…”

Section: Yusuf Yagci Is a Professor Of Chemistry At Istanbul Technicamentioning

confidence: 99%

Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems

Çiftçi

Taşdelen

Yaǧcı

2016

Polymer International

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The environmentally friendly Mn 2 (CO) 10 -based visible light photoinitiating system is a powerful method for the preparation of linear and crosslinked polymeric structures. From a practical point of view, the most important feature of this initiating system is its optical characteristics in the visible range with high quantum yield and good solubility properties. This photoinitiating system is applicable for a variety of monomers that can be polymerized via either radical or cationic mechanisms. Various complex macromolecular structures such as telechelic polymers, block and graft copolymers, polymer networks and surface modifications can be simply prepared by using halogenated precursors. This photoinitiating system is also combined with controlled radical polymerization techniques providing a mild and efficient method for polymer synthesis.

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Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings

Cited by 70 publications

References 28 publications

Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn₂(CO)₁₀and Visible Light

Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems

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Initiation of radical cyclisation reactions using dimanganese decacarbonyl. A flexible approach to preparing 5-membered rings

Cited by 70 publications

References 28 publications

Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

Origins of Initiation Rate Differences in Ruthenium Olefin Metathesis Catalysts Containing Chelating Benzylidenes

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn2(CO)10and Visible Light

Macromolecular design and application using Mn2(CO)10‐based visible light photoinitiating systems

Contact Info

Product

Resources

About

Photochemically Enabled Iodine Degenerative Transfer Controlled Radical Homo- and Block Copolymerization of Vinylidene Fluoride at Ambient Temperatures with Mn₂(CO)₁₀and Visible Light

Macromolecular design and application using Mn₂(CO)₁₀‐based visible light photoinitiating systems