No-D NMR Spectroscopy as a Convenient Method for Titering Organolithium (RLi), RMgX, and LDA Solutions

Hoye, Thomas R.; Eklov, Brian M.; Voloshin, M.B.

doi:10.1021/ol049145r

Cited by 63 publications

(49 citation statements)

References 15 publications

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“…was added, followed by stirring for another 30 min at 40 – 50 °C. Prior to use, the reagent was analyzed by titration against salicylaldehyde phenylhydrazone or by qNMR with an internal standard (1,5‐cyclooctadiene) and a C 6 D 6 capillary for locking purposes . 1 H‐NMR (500 MHz, Et 2 O; C 6 D 6 ‐capillary): −0.14 ( t , J = 8.1, 2 H); 1.27 ( t , J = 6.8, 3 H); 1.63 – 1.74 ( m , 10 H); 1.87 – 1.95 ( m , 2 H).…”

Section: Methodsmentioning

confidence: 99%

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Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Brunner

Hintermann

2016

Helvetica Chimica Acta

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An asymmetric catalytic total synthesis of (S)‐10‐hydroxystearic acid (1) for comparison of its absolute configuration to that of samples obtained by fermentative hydration of oleic acid is reported. The synthesis involves two catalytic key‐steps, namely Ru‐catalyzed anti‐Markovnikov hydration of 9‐decynoic acid (7) to 10‐oxodecanoic acid (5), followed by titanium‐mediated asymmetric catalytic addition of dioctylzinc (25) to 5 in presence of the chiral ligand N,N’‐((1R,2R)‐cyclohexane‐1,2‐diyl)bis(1,1,1‐trifluoromethanesulfonamide) (6). The synthesis is short and efficient and avoids use of protecting groups. Ozonolysis of 10‐undecynoic acid (9) to 5 provides an alternative entry point into the synthetic route. The double dehydrobromination of (ω,ω‐1)‐dibromoalkanoic acids to ω‐alkynoic acids under a variety of conditions was investigated with 10,11‐dibromoundecanoic acid (11) as model substrate and using qNMR to quantify all reaction products. The synthetic approaches presented here have the potential to be generalized to the asymmetric catalytic synthesis of a variety of n‐hydroxy‐fatty acids.

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Section: Methodsmentioning

confidence: 99%

“…The content of the reagent was determined by titration with I 2 –LiCl soln . or by qNMR with 1,5‐cyclooctadiene as internal standard . 1 H‐NMR (500 MHz, PhMe; C 6 D 6 ‐capillary): 0.37 ( t , J = 5.8, 4 H); 0.90 – 0.95 ( m , 6 H); 1.13 – 1.35 ( m , 20 H); 1.55 – 1.65 ( m , 4 H).…”

Section: Methodsmentioning

confidence: 99%

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Brunner

Hintermann

2016

Helvetica Chimica Acta

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“…In addition, the ability to perform shimming on all the available shims of a magnet as opposed to just the Z shims, which deuterium shimming is generally limited to, is a major advantage. (For examples of the application of ‘No‐D’ (no deuterium) spectroscopy in organic chemistry, see the work of Hoye) …”

Section: Challenges For the Use Of Nmr Spectroscopy In Ionic Liquids mentioning

confidence: 99%

NMR spectroscopy to follow reaction progress in ionic liquids

Butler

Thomas

Hook

et al. 2014

Magnetic Reson in Chemistry

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In order to understand reaction outcomes in ionic liquids, it is crucial to be able to follow the progress of these reactions. This review highlights the advantages of NMR spectroscopy over other analytical techniques in following reaction progress in ionic liquids, particularly addressing the practical aspects of the methodology and highlighting the range of processes that can be readily followed. Copyright © 2014 John Wiley & Sons, Ltd.

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“…Analogues 7, 8, and 13-25 were synthesized according to theses routes in yields ranging from 52-93% (Scheme 2 and 4). Higher yields were obtained utilizing a freshly distilled THF solution and accurately determining nBuLi concentration through titration or NMR analysis, 25 as previously reported. Analogue 9 was constructed via imine condensation providing the product in 96% yield (Scheme 3).…”

Section: Resultsmentioning

confidence: 66%

Discovery of diphenyl amine based sodium channel blockers, effective against hNav1.2

Hudgens

Taylor

Batts

et al. 2006

Bioorganic & Medicinal Chemistry

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The development of new therapies for chronic pain is an area of unmet medical need. Central to pathways of chronic pain is the upregulation of voltage gated sodium channels. The use of tricyclic antidepressants, which also have sodium channel activity, in chronic pain therapy prompted us to develop novel compounds from this scaffold. Herein, we show that the tricyclic moiety is not needed for effective inhibition of the [ 3 H]-BTX binding site and sodium currents of hNa v 1.2. Our lead compound (6), containing a diphenyl amine motif demonstrated a 53.2% inhibitory block of Na v 1.2 current at 10 μM, which is greater than 50% increase in current block in comparison to the amitriptyline standard. Altogether our study establishes that the tricyclic motif is unnecessary for hNa v 1.2 activity and modification of the amine portion is detrimental to sodium channel block.

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No-D NMR Spectroscopy as a Convenient Method for Titering Organolithium (RLi), RMgX, and LDA Solutions

Cited by 63 publications

References 15 publications

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

Configurational Assignment of ‘Cryptochiral’ 10‐Hydroxystearic Acid Through an Asymmetric Catalytic Synthesis

NMR spectroscopy to follow reaction progress in ionic liquids

Discovery of diphenyl amine based sodium channel blockers, effective against hNav1.2

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