Direct Conversion of Aldehydes and Ketones into Azides by Sequential Nucleophilic Addition and Substitution

Goswami, Pratik P.; Suding, Victoria P.; Carlson, Angela S.; Topczewski, Joseph J.

doi:10.1002/ejoc.201600856

Cited by 18 publications

(26 citation statements)

References 38 publications

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“…Since this seminal work, others have used the Winstein rearrangement synthetically, however it has not seen broad application . We recently initiated a program to further explore the potential utility of this dynamic system , . Central to our goal of harnessing the Winstein rearrangement is understanding the fundamental properties that govern this process.…”

Section: Introductionmentioning

confidence: 99%

The Effect of Proximal Functionality on the Allylic Azide Equilibrium

et al. 2017

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This report describes an investigation into the effect that proximal functionality has on the allylic azide equilibrium. We report 16 allylic azides with varied functionality from three subclasses. We observe a correlation of % branched azide to the pKa of the OR group. We also observe that RN–H azides have a higher % branched azide relative the corresponding RN–Bn compound. These two effects combine to describe the observed equilibrium for the known compound hydroxy‐crotyl azide. DFT calculations support several stereoelectronic effects that contribute to the relative energetics.

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Section: Introductionmentioning

confidence: 99%

The Effect of Proximal Functionality on the Allylic Azide Equilibrium

et al. 2017

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“…The naphthyl containing compound was studied because the isomers were separable by column chromatography. 42 We conducted a kinetic analysis of the E to Z isomerization by 1 H NMR at 75 °C in C 6 D 6 . The observed rate constant ( k 1 + k −1 ) was 7.2 × 10 −4 s −1 and the observed ratio of 23 : 24 was 3.2:1 at equilibrium (equilibrium reached after 90 min).…”

Section: Resultsmentioning

confidence: 99%

“…Using a known procedure 42 the product was isolated (520 mg, 65%). Characterization data for this compound has been reported.…”

Section: Methodsmentioning

confidence: 99%

Evidence for a Sigmatropic and an Ionic Pathway in the Winstein Rearrangement

et al. 2018

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The spontaneous rearrangement of allylic azides is thought to be a sigmatropic reaction. Presented herein is a detailed investigation into the rearrangement of several allylic azides. A combination of experiments including equilibrium studies, kinetic analysis, density functional theory calculations, and selective N-isotopic labeling are included. We conclude that the Winstein rearrangement occurs by the assumed sigmatropic pathway under most conditions. However, racemization was observed for some cyclic allylic azides. A kinetic analysis of this process is provided, which supports a previously undescribed ionic pathway.

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“…72 To make some allylic azides more readily accessible, Topczewski and co-workers developed a method to convert aldehydes and ketones directly into their corresponding azides (Scheme 5b). 73 Grignard addition generated an alkoxide in situ and subsequent addition of DPPA produced the azide without isolation of the intermediate alcohol or phosphate. The scope of this method includes the formation of allylic azides from vinyl magnesium chloride addition or addition to an enal/enone.…”

Section: Allylic Azide Synthesis Substitutionmentioning

confidence: 99%