Synthesis of secondary and tertiary amides without coupling agents from amines and potassium acyltrifluoroborates (KATs)

Schuhmacher, Anne; Shiro, Tomoya; Ryan, Sarah J.; Bode, Jeffrey W.

doi:10.1039/d0sc01330g

Cited by 18 publications

(14 citation statements)

References 52 publications

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“…Interestingly, a one-pot reaction was later developed by the same group, in which KATs and amines were first reacted to provide TIMs, which were further oxidized with aqueous H 2 O 2 to provide amides ( Scheme 8 , entry 1b). 26 The authors suggested that the reaction proceeded by the addition of peroxide to the TIM and subsequent elimination of the trifluoroborate. This method allowed the synthesis of tertiary amides that would otherwise be inaccessible by the ligation reactions described above and was shown to allow modification of peptides.…”

Section: New Applications Of Acylboranesmentioning

confidence: 99%

Recent Advances in the Synthesis of Acylboranes and Their Widening Applicability

2020

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The most common types of acylboranes are acyltrifluoroborates, acyl MIDA-boronates, and monofluoroacylboronates. Because of the increasing importance of these compounds in the past decade, we highlight the recently reported synthetic strategies to access acylboranes. In addition, an expanding array of their applications has been discovered, based on either the ability of acylboranes to enter rapid amide-forming ligations or the retained ketone-like character of the carbonyl group. Therefore, we also describe ground-breaking achievements where acylboranes were successfully put to use, such as their utility in biochemical, material, and medicinal sciences.

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Section: New Applications Of Acylboranesmentioning

confidence: 99%

Recent Advances in the Synthesis of Acylboranes and Their Widening Applicability

2020

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“…[21] Instead of using hydroxylamines or azides as the amine donor,t he toolbox toward amide formation with acyltrifluoroborates was further expanded to in situ generated chloroamines [22] or oxidation of KAT-iminiums with peroxide (Scheme 4b). [23] Dino Wu TheK AT ligation was furthermore utilized in the formation of PEG-based hydrogels. [24] Encapsulation of bovine chondrocytes through these hydrogels further showcased the biocompatibility of the acyltrifluoroborate group (Scheme 5).…”

Section: Synthetic Applications Of Acylboronate Derivativesmentioning

confidence: 99%

“…N‐protected glycines and a Cbz‐protected l ‐alanine analog were prepared without racemization. These α‐amino acylborons could become building blocks for the synthesis of peptides, as shown by their conversion to the corresponding KATs and preliminary efforts towards oligopeptide synthesis …”

Section: Synthesis From Oxidative Strategiesmentioning

confidence: 99%

“…By attaching desthiobiotin to both hydroxylamine 6 and monofluoro acylboronates 7 and using streptavidin as a template, ligation at submicromolar concentrations occurs efficiently (Scheme a) . Instead of using hydroxylamines or azides as the amine donor, the toolbox toward amide formation with acyltrifluoroborates was further expanded to in situ generated chloroamines or oxidation of KAT‐iminiums with peroxide (Scheme b) …”

Section: Introductionmentioning

confidence: 99%

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Synthesis of Acylboron Compounds

Taguchi

Tanriver

et al. 2020

Angewandte Chemie

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Acylboron compounds are emerging as versatile functional groups with applications in multiple research fields. Their synthesis, however, is still challenging and requires innovative methods. This Minireview provides an overview on the obstacles of acylboron synthesis and highlights notable advances within the last three years on new strategies to overcome the challenges posed by the formation of acyl–boron bonds.

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“…Das N , N ‐Dimethylamin‐TIM, welches während der Kreuzkupplung mit 1 erhalten wurde, konnte mit einem anderen Amin ausgetauscht werden, um andere tertiäre Amide zu bilden (Schema 3 b). [2, 3, 18] …”

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Katalytische Synthese von Kaliumacyltrifluoroboraten (KATs) aus Boronsäuren und dem Thioimidat‐KAT‐Transferreagenz

2020

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Wir berichten über die Synthese von Kaliumacyltrifluoroboraten (KATs) mittels Palladium‐katalysierter Kreuzkupplung von Boronsäuren mit dem Thioimidat‐KAT‐Transferreagenz. Die Kombination von breit erhältlichen Aryl‐ und Vinylboronsäuren mit kommerziellem Thioimidat 1 unter Verwendung von katalytischem PdII und CuII als Additiv erlaubt die Herstellung von KATs in hohen Ausbeuten und mit guter Verträglichkeit für verschiedene funktionelle Gruppen. Das formale Einfügen von CO in Organoboronsäuren kann unter Verwendung eines geringfügig veränderten Vorgehens auch für Boronsäurepinakolester und Kaliumorganotrifluoroborate angewendet werden. Durch die einzigartige Chemie von KATs und Trifluoroboratiminiumionen (TIMs) lassen sich Kreuzkupplungen auch auf die Synthese von Amiden und α‐Aminotrifluoroboraten als Eintopfvariante ausweiten.

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Synthesis of secondary and tertiary amides without coupling agents from amines and potassium acyltrifluoroborates (KATs)

Abstract: Oxidative amidation of potassium acyltrifluoroborates (KATs) and amines via trifluoroborate iminiums (TIMs) delivers amides without coupling agents. This unusual approach to amides can be applied for the late-stage modification of bioactive molecules and for solid-phase peptide synthesis.

Cited by 18 publications

References 52 publications

Recent Advances in the Synthesis of Acylboranes and Their Widening Applicability

Recent Advances in the Synthesis of Acylboranes and Their Widening Applicability

Synthesis of Acylboron Compounds

Katalytische Synthese von Kaliumacyltrifluoroboraten (KATs) aus Boronsäuren und dem Thioimidat‐KAT‐Transferreagenz

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