Über die Synthese von α‐Azidoestern und geminalen Triaziden

Klahn, Philipp; Erhardt, Hellmuth; Kotthaus, Andreas; Kirsch, Stefan F.

doi:10.1002/ange.201402433

Cited by 25 publications

(1 citation statement)

References 98 publications

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“…Fort he azidation of carbonyl compounds,K irsch and coworkers also developed an alternative method based on the use of sodium azide and ac yclic l-5-iodane,I BX-SO 3 K. [38] This method was efficient for the azidation and diazidation of dicarbonyl compounds,a swell as for the synthesis of atriazido ketones.…”

Section: Methodsmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

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Hypervalent iodine compounds are privileged reagents in organic synthesis because of their exceptional reactivity. Among these compounds, cyclic derivatives stand apart because of their enhanced stability. They have been widely used as oxidants, but their potential for functional‐group transfer has only begun to be investigated recently. The use of benziodoxol(on)es for trifluoromethylation (Togni's reagents) is already widely recognized, but other transformations have also attracted strong interest recently. In this Review, the development in the area since 2011 will be presented. After a short summary of synthetic methods to prepare benziodoxol(on)e reagents, their use to construct carbon–heteroatom and carbon–carbon bonds will be presented. In particular, the introduction of alkynes by using ethynylbenziodoxol(on)e (EBX) reagents has been highly successful. Breakthroughs in the introduction of alkoxy, azido, difluoromethyl, and cyano groups will also be described.

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Section: Methodsmentioning

confidence: 99%

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

et al. 2016

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Manganese‐Dioxide‐Catalyzed Trifluoromethylation and Azidation of Styrenyl Olefins via Radical Intermediates

2017

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Am anganese-dioxide-catalyzed trifluoromethylation of styrenes and enol acetates using the Langlois reagent is reported. Employing oxygen/air as the oxidant, styrenes afforded am ixture of the trifluoromethylacohol and ketone products in good overall yields. The protocol also works successfully for converting a-methylstyrened erivatives to the corresponding trifluoromethyl alcohols. The keto-trifluoromethylated products could be obtained exclusively when using enol acetates as substrates under the same reaction conditions. The method was extended to the radical azidationo fe nol acetates using trimethylsilyl azide to furnish the corresponding azido-ketones in good yields.Catalytic strategies for olefin functionalization form av ersatile repertoire of reactions using whichadiversea rray of functionalities can be generated. [1] The applicationo ff irst row transition metal catalysts forf unctionalization of olefins via free radical pathways has been an attractive synthetic pathway to explore, as demonstrated by recently reported elegant studies. [2] Amongt he many challenges, the controlo fo xidation state outcome, application of minimally functionalized olefins, and the development of inexpensive catalyst systems remaina tt he forefront. In this context,t he trifluoromethylation of olefins has been studied extensively with many catalysts including Cu, [3] Fe, [4] Pd, [5] Ag, [6] Ru, [7] and photoredox systems. [8] Oxidative trifluoromethylations employing as ilver catalystw ith various oxidants have also been reported. [9] Given the rich chemistry of manganese in Nature as well as in synthetic systems, [10] we were interestedi nd eveloping radicalt rifluoromethylation [11] and azidation [2k, 12] of olefins using readily available reagents and inexpensivec atalyst [2a, j, k, 13] which could operate in conditions that didn ot involve stoichiometrica mountso fa dditives [2a, b] and oxidants such as peroxides. [2c, 14] We selected vinyl naphthalene for optimizations tudy and performed variouse xperiments to ascertain the best condi- [a] Scheme1.Oxytrifluoromethylation reaction scope.Reactionconditions: styrenederivative (1 equiv.), CF 3 SO 2 Na (2 equiv.), MnO 2 (0.2 equiv.), and K 2 S 2 O 8 (0.2 equiv.) werec ombined in DMF (2 mL) and stirreda tr tf or 6-24 hours.Scheme2.Reactionscope: a-methylstyrenes. Isolated yields are reported.[a] Reaction performed under air.

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(Diacetoxyiodo)benzene‐mediated Selective Synthesis of α‐Azido Ketones or Acyl Azides from β‐Keto Acids

Zheng

et al. 2018

Asian J Org Chem

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Abstract(Diacetoxyiodo)benzene‐mediated selective synthesis of α‐azido ketones or acyl azides from keto acids is developed. The selectivity depends on the amounts of the reagents used. Treatment of β‐keto acid derivatives with 1.2 or 2.2 equivalents of (diacetoxyiodo)benzene results in α‐azido ketone or acyl azide products, respectively. Initial mechanistic studies show that monobromomethyl ketone and dibromomethyl ketone are plausible intermediates in these reactions.

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Über die Synthese von α‐Azidoestern und geminalen Triaziden

Cited by 25 publications

References 98 publications

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Cyclic Hypervalent Iodine Reagents for Atom‐Transfer Reactions: Beyond Trifluoromethylation

Manganese‐Dioxide‐Catalyzed Trifluoromethylation and Azidation of Styrenyl Olefins via Radical Intermediates

(Diacetoxyiodo)benzene‐mediated Selective Synthesis of α‐Azido Ketones or Acyl Azides from β‐Keto Acids

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