Prevention of Undesirable Isomerization during Olefin Metathesis

Hong, Soon Hyeok; Sanders, Daniel P.; Lee, Choon Woo; Grubbs, Robert H.

doi:10.1021/ja052939w

Cited by 621 publications

(511 citation statements)

References 11 publications

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“…[20] Pre-catalyst 2 is known to favour metathesis over isomerisation, [21] with isomerisation common with "stressed" catalysts arising from high reaction temperatures, high dilution or forced high turnover. [22] None of these factors would appear to be relevant to the RCM reactions of 1 c reported here. The 1 H NMR spectrum of a concentrated reaction ([1 c] 0 = 2 m in CDCl 3 ) does contain a peak consistent with the presence of diruthenium hydride 6 at À8.77 ppm (lit.…”

Section: Resultsmentioning

confidence: 83%

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

Nelson

Ashworth

Hillier

et al. 2011

Chemistry A European J

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The thermodynamic effective molarities of a series of simple cycloalkenes, synthesised from α,ω‐dienes by reaction with Grubbs’ second generation precatalyst, have been evaluated. Effective molarities were measured from a series of small scale metathesis reactions and agreed well with empirical predictions derived from the number of rotors and the product ring strain. The use of electronic structure calculations (at the M06‐L/6‐311G** level of theory) was explored for predicting thermodynamic effective molarities in ring‐closing metathesis. However, it was found that it was necessary to apply a correction to DFT‐derived free energies to account for the entropic effects of solvation.

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Section: Resultsmentioning

confidence: 83%

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

Nelson

Ashworth

Hillier

et al. 2011

Chemistry A European J

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“…To our delight, the pivotal RCM proceeded readily by using the Grubbs second‐generation catalyst8 in the presence of 1,4‐benzoquinone9 to yield the desired product 12 in 83 % yield as a 9:1 mixture of trans and cis isomers (Scheme 4). …”

Section: Resultsmentioning

confidence: 99%

Structure‐Enabled Discovery of a Stapled Peptide Inhibitor to Target the Oncogenic Transcriptional Repressor TLE1

McGrath

Tortorici

Drouin

et al. 2017

Chemistry A European J

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TLE1 is an oncogenic transcriptional co‐repressor that exerts its repressive effects through binding of transcription factors. Inhibition of this protein–protein interaction represents a putative cancer target, but no small‐molecule inhibitors have been published for this challenging interface. Herein, the structure‐enabled design and synthesis of a constrained peptide inhibitor of TLE1 is reported. The design features the introduction of a four‐carbon‐atom linker into the peptide epitope found in many TLE1 binding partners. A concise synthetic route to a proof‐of‐concept peptide, cycFWRPW, has been developed. Biophysical testing by isothermal titration calorimetry and thermal shift assays showed that, although the constrained peptide bound potently, it had an approximately five‐fold higher K d than that of the unconstrained peptide. The co‐crystal structure suggested that the reduced affinity was likely to be due to a small shift of one side chain, relative to the otherwise well‐conserved conformation of the acyclic peptide. This work describes a constrained peptide inhibitor that may serve as the basis for improved inhibitors.

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“…Olefin isomerization due to degradation products of the Grubbs catalyst could lead to the observed side products [6].…”

Section: Introductionmentioning

confidence: 99%

“…Here, we present the results of different strategies to minimize the side reaction, including examination of reagents reported to suppress isomerization [6,7] as well as microwave heating.…”

Section: Introductionmentioning

confidence: 99%

Peptide Ring Closing Metathesis: Minimizing Side Reactions in Arodyn Analogs

Gisemba¹,

Aldrich²

2015

Peptides 2015, Proceedings of the 24th American Peptide Symposium

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Prevention of Undesirable Isomerization during Olefin Metathesis

Abstract: General Considerations.Manipulation of organometallic compounds was performed using

Cited by 621 publications

References 11 publications

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

Why is RCM Favoured Over Dimerisation? Predicting and Estimating Thermodynamic Effective Molarities by Solution Experiments and Electronic Structure Calculations

Structure‐Enabled Discovery of a Stapled Peptide Inhibitor to Target the Oncogenic Transcriptional Repressor TLE1

Peptide Ring Closing Metathesis: Minimizing Side Reactions in Arodyn Analogs

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