Electrophilic Amination: The Case of Nitrenoids

Starkov, Pavel; Jamison, Timothy F.; Marek, Ilan

doi:10.1002/chem.201405779

Cited by 73 publications

(25 citation statements)

References 140 publications

(100 reference statements)

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“…In more recent years, much attention has been paid to catalytic, direct arene aminations (17–19). Many elegant atom- and step-efficient protocols have been introduced, but virtually all require a directing group while others need an excess of arene, high temperatures, or generate amides, imides, and sulfomamides instead of free amines (20–31).…”

Section: Main Textmentioning

confidence: 99%

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Paudyal

Adebesin

Burt

et al. 2016

Science

247

139

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Primary and N-alkyl arylamine motifs are key functional groups in pharmaceuticals, agrochemicals and functional materials as well as in bioactive natural products. However, there is a dearth of generally applicable methods for the direct replacement of aryl hydrogens with –NH2/-NH-alkyl moieties. Here, we present a mild dirhodium-catalyzed C-H amination for conversion of structurally diverse monocyclic and fused aromatics to the corresponding primary and N-alkyl arylamines using either NH2/NHalkyl-O-(sulfonyl)hydroxylamines as aminating agents; the relatively weak RSO2O-N bond functions as an internal oxidant. The methodology is operationally simple, scalable, and fast at or below ambient temperature, furnishing arylamines in moderate-to-good yields and with good regioselectivity. It can be readily extended to the synthesis of fused N-heterocycles.

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Section: Main Textmentioning

confidence: 99%

Dirhodium-catalyzed C-H arene amination using hydroxylamines

Paudyal

Adebesin

Burt

et al. 2016

Science

247

139

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“…To furthere xplore the robustness of the transformation, and the compatibility of the reactionc onditions, additives werea dded to the reactiona nd their recovery and the product yield in their presence analyzed (Table 4). In analogy to our previousw ork, we expect the transformation to proceed via ab orate-induced ([B 2 pin 2 ·R] À À ) two-step reductiono ft he nitro group via nitronate A to as hort-lived nitrenoid B, [13] which serves as the electrophilicn itrogen source (Scheme 3). The investigation startedw ith the addition of strong electrophiles.…”

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confidence: 82%

Direct Reductive N‐Functionalization of Aliphatic Nitro Compounds

Rauser

Ascheberg

Niggemann

2018

Chemistry A European J

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The first general protocol for the direct reductive N-functionalization of aliphatic nitro compounds is presented. The nitro group is partially reduced to a nitrenoid, with a mild and readily available combination of B pin and zinc organyls. Thereby, the formation of an unstable nitroso intermediate is avoided, which has so far severely limited reductive transformations of aliphatic nitro compounds. The reaction is concluded by an electrophilic amination of zinc organyls.

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“…As the catalytic asymmetric carbometalation reaction of cyclopropenes 1 provides au nique entry to cyclopropylmagnesium species 2,wewere also interested in using this strategy to prepare the challenging enantioenriched cyclopropylamine derivatives 4.Among the available sources for sp 3 -hybridized nitrogen electrophiles to be used in electrophilic amination reactions, [17] we were particularly interested in the reactivity of nitrenoids [18] as well as O-benzoyl hydroxylamine derivatives. [19] Whereas all our efforts at electrophilic amination with nitrenoids failed to produce the expected cyclopropylamine derivatives in decent yields,cyclopropylcopper species, easily obtained from at ransmetalation reaction of 2 with CuCN·2 LiCl in THF,r eacted smoothly with various O-benzoyl hydroxylamines to provide the expected cyclopropylamines 4 in good yields and high enantioselectivity as single diastereomers (Scheme 3).…”

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confidence: 99%