Reductive Csp2–N Coupling by PIII/PV=O–Catalysis

Li, Gen; Grotenhuis, Colet te; Radosevich, Alexander T.

doi:10.1016/j.trechm.2020.10.001

Cited by 12 publications

(11 citation statements)

References 10 publications

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“…This pathway is predicted to outcompete evolution of the oxazaphosphirane to free nitrene 60, accounting for the excellent selectivity for intermolecular cross-coupling. 275,276 The C−N coupling event can be telescoped with subsequent ring closing events to allow for the synthesis of N-aryl heterocycles (58) by a cross-coupling/condensation cascade, as depicted in Figure 22. 277 Phosphetane oxide P4•[O] also efficiently catalyzes deoxygenative processing of sulfonyl chlorides (including trifluoromethyl-and heteroarylsulfonyl derivatives) by Oatom transfer (Figure 23).…”

Section: State-of-the-art Developments Inmentioning

confidence: 99%

“…Mechanistic investigations support a pathway involving formation of the oxazaphosphirane intermediate P4b , followed by engagement with the boronic acid 57 to make betaine P4c , leading to product formation via 1,2-metallate shift. This pathway is predicted to outcompete evolution of the oxazaphosphirane to free nitrene 60 , accounting for the excellent selectivity for intermolecular cross-coupling. , The C–N coupling event can be telescoped with subsequent ring closing events to allow for the synthesis of N-aryl heterocycles ( 58 ) by a cross-coupling/condensation cascade, as depicted in Figure…”

Section: State-of-the-art Developments In Organopnictogen Redox Catal...mentioning

confidence: 99%

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Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

2021

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A growing number of organopnictogen redox catalytic methods have emergedespecially within the past 10 yearsthat leverage the plentiful reversible two-electron redox chemistry within Group 15. The goal of this Perspective is to provide readers the context to understand the dramatic developments in organopnictogen catalysis over the past decade with an eye toward future development. An exposition of the fundamental differences in the atomic structure and bonding of the pnictogens, and thus the molecular electronic structure of organopnictogen compounds, is presented to establish the backdrop against which organopnictogen redox reactivityand ultimately catalysisis framed. A deep appreciation of these underlying periodic principles informs an understanding of the differing modes of organopnictogen redox catalysis and evokes the key challenges to the field moving forward. We close by addressing forward-looking directions likely to animate this area in the years to come. What new catalytic manifolds can be developed through creative catalyst and reaction design that take advantage of the intrinsic redox reactivity of the pnictogens to drive new discoveries in catalysis?

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Section: State-of-the-art Developments Inmentioning

confidence: 99%

Section: State-of-the-art Developments In Organopnictogen Redox Catal...mentioning

confidence: 99%

Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

2021

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“…The use of nitro compoundsspecifically nitroarenesas direct partners in catalytic reductive C–N coupling represents an important emerging mode of direct N -functionalization for these common substrates (Figure A). − By contrast, the catalytic reductive N -functionalization of nitroalkanes has been substantially less developed; notable exceptions include a B 2 pin 2 -mediated reductive N -alkylation of nitroalkanes with organozinc nucleophiles and a triphenylphosphine-mediated reductive N -arylation of nitroalkanes catalyzed by an oxomolybdenum(VI) compound under microwave irradiation . In order to more generally reveal the reactivity of readily accessible nitroalkanes as convenient and easy-to-handle masked amine precursors for C–N coupling chemistry, we report here a new catalytic methoddriven by redox cycling in the P(III)/P(V)O manifoldthat results in selective C–N bond formation between highly functionalized nitroalkanes and arylboronic acids (Figure B).…”

Section: Introductionmentioning

confidence: 99%

Enabling Reductive C–N Cross-Coupling of Nitroalkanes and Boronic Acids by Steric Design of P(III)/P(V)═O Catalysts

Kanda

Hong

et al. 2022

J. Am. Chem. Soc.

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An organophosphorus-catalyzed C−N bond-forming reductive coupling of nitroalkanes with arylboronic acids and esters is reported. The method shows excellent chemoselectivity for the nitro/boronic acid substrate pair, allowing the synthesis of N-(hetero)arylamines rich in functionalization. The identification of a sterically reduced phosphetane catalyst capable of productive coupling in the P(III)/P(V)O redox manifold is the key enabling development. Combined experimental kinetics and computational mechanistic studies show that the sterically reduced catalyst affects post-rate-limiting steps to enable the C−N coupling event in preference to deleterious side-paths.

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“…However the use of stoichiometric amounts of Ph 3 P will diminish the total reaction economy, leading to issues in purification, and the aliphatic carboxylic acids remain challenging substrates with Ph 3 P as deoxygenation reagent under photoredox conditions due to the possibility of their decarboxylation 38 – 41 . Inspired by Radosevich’s recent seminal work on the P(III)/P(V) catalytic cycle 25 , 42 – 46 , we questioned if Umpolung amidation of carboxylic acids is possible with electrophilic amination reagents of nitroarenes. Such a reaction could proceed by means of synergistic photoredox and R 3 P/R 3 P = O catalysis, where the generated nucleophilic acyl radical undergoes radical addition to electrophilic amination reagents as shown in Fig.…”

Section: Introductionmentioning

confidence: 99%

Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

Ning

Wang

et al. 2021

Nat Commun

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Development of catalytic amide bond-forming methods is important because they could potentially address the existing limitations of classical methods using superstoichiometric activating reagents. In this paper, we disclose an Umpolung amidation reaction of carboxylic acids with nitroarenes and nitroalkanes enabled by the triplet synergistic catalysis of FeI2, P(V)/P(III) and photoredox catalysis, which avoids the production of byproducts from stoichiometric coupling reagents. A wide range of carboxylic acids, including aliphatic, aromatic and alkenyl acids participate smoothly in such reactions, generating structurally diverse amides in good yields (86 examples, up to 97% yield). This Umpolung amidation strategy opens a method to address challenging regioselectivity issues between nucleophilic functional groups, and complements the functional group compatibility of the classical amidation protocols. The synthetic robustness of the reaction is demonstrated by late-stage modification of complex molecules and gram-scale applications.

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Reductive Csp2–N Coupling by PIII/PV=O–Catalysis

Cited by 12 publications

References 10 publications

Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

Main Group Redox Catalysis of Organopnictogens: Vertical Periodic Trends and Emerging Opportunities in Group 15

Enabling Reductive C–N Cross-Coupling of Nitroalkanes and Boronic Acids by Steric Design of P(III)/P(V)═O Catalysts

Site-specific Umpolung amidation of carboxylic acids via triplet synergistic catalysis

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