Iron‐Catalyzed CH and CC Bond Cleavage: A Direct Approach to Amides from Simple Hydrocarbons

Qin, Chong; Zhou, Wang; Chen, Feng; Ou, Yang; Jiao, Ning

doi:10.1002/ange.201106112

Cited by 49 publications

(5 citation statements)

References 130 publications

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“…18 A direct approach to amides from benzyl hydrocarbons was achieved through iron-catalysed reaction utilizing TMSN 3 and DPPA as an azide source. 19 Diphenylmethane (20) afforded N-phenylbenzamide (21) by thermal treatment with FeCl 2 , DDQ, TMSN 3 , DPPA, H 2 O, HOAc, and TFA under argon in good yield, as shown in Scheme 7. The same reaction conditions applied to the ring expansion of 5-7 membered ring benzyl-type hydrocarbons.…”

Section: Organic Chemistry Frontiers Reviewmentioning

confidence: 99%

Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

2022

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Section: Organic Chemistry Frontiers Reviewmentioning

confidence: 99%

Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

2022

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“…In 2011, Jiao and co-workers reported a transformation of benzyl hydrocarbons 24 into the corresponding amides 28 using a tandem iron-catalyzed oxidative substitution/rearrangement reaction (Scheme 8). 16 In wet protonic acid, iron-assisted oxidative addition with TMSN 3 in the presence of DDQ formed 25 which subsequently undergoes a highly chemoselective Beckmann rearrangement followed by hydrolysis resulting in the formation of amide 28. Six-and seven-membered rings could also be converted into the corresponding lactams in good yields.…”

Section: Monodentate Ligand Chelationassisted C(aryl)-c(sp 3 ) Bond Cmentioning

confidence: 99%

Recent progress in C(aryl)–C(alkyl) bond cleavage of alkylarenes

et al. 2020

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“…The allyl cation intermediate is also involved in other nitrogenation reactions developed by us (Scheme ) . The cation would be attacked by azide to form allylic azide cation A under oxidative conditions.…”

Section: Direct Oxidative Transformation Of Allylarenes or Alkenes To...mentioning

confidence: 99%

Direct Approaches to Nitriles via Highly Efficient Nitrogenation Strategy through C–H or C–C Bond Cleavage

2014

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Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our synthetic strategy more attractive. Our direct nitrile synthesis methodologies have potential applications in the synthesis of biologically active molecules and drug candidates.

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Iron‐Catalyzed CH and CC Bond Cleavage: A Direct Approach to Amides from Simple Hydrocarbons

Cited by 49 publications

References 130 publications

Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

Cutting edge of diphenyl phosphorazidate (DPPA) as a synthetic reagent – A fifty-year odyssey

Recent progress in C(aryl)–C(alkyl) bond cleavage of alkylarenes

Direct Approaches to Nitriles via Highly Efficient Nitrogenation Strategy through C–H or C–C Bond Cleavage

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