Iron-catalysed 1,2-aryl migration of tertiary azides

Wei, Kai‐Jie; Chen, Qing; Liang, Siyu; Yu, Wei

doi:10.1039/d0cc04579a

Cited by 11 publications

(9 citation statements)

References 55 publications

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“…The most important among them are the Curtius and Schmidt rearrangements . Benzylic azides are known to rearrange via [1,2]-aryl shift under strongly acidic conditions to form an N -aryl iminium ion ( I ) (Figure A), , which can be trapped by a variety of nucleophiles in situ. This type of reactivity has been pioneered by Pearson and Fang and exploited for the construction of various nitrogen-containing organic compounds (Figure B).…”

Section: Introductionmentioning

confidence: 99%

Fluorine-Assisted Rearrangement of Geminal Azidofluorides to Imidoyl Fluorides

2023

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Organoazide rearrangement constitutes versatile synthetic strategies but typically requires an extremely strong acid and/or a high reaction temperature. Our group recently discovered the remarkable accelerating effect of the geminal fluorine substituent that enables the facile rearrangement of azides into imidoyl fluorides without the aid of acid under much milder reaction conditions. The role of geminal fluorine was elucidated by both experimental and computational investigations. This new reactivity led to the development of a practical one-step tandem preparative method for potentially useful and bench-stable imidoyl fluorides from a wide range of structurally diverse geminal chlorofluorides. Our additional efforts to expand the reaction scope regarding the migrating group, halogen, and carbonyl function are described, and the synthetic utility of the imidoyl fluoride products was demonstrated in hopes of promoting the use of this under-appreciated functional group in the synthetic organic community.

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Section: Introductionmentioning

confidence: 99%

Fluorine-Assisted Rearrangement of Geminal Azidofluorides to Imidoyl Fluorides

2023

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“…These compounds have been well-recognized in the area of medicinal chemistry, and many α,α′-diarylmethyl amine-based drugs have been already commercialized (Figure ). , Numerous synthetic methods have been established to access α,α′-diarylmethyl amine or carbamate derivatives, including the arylation of imines, − the amination of diarylmethanols, − benzylic C–H amination via cross-dehydrogenative coupling, , the Lossen rearrangement of hydroxamic acids, , the reduction and transfer hydrogenation of imines, − the direct reductive amination of ketones, − the aryl migration of azides, desulfonylative amination, etc. A few other protocols have also been reported for the preparation of diarylmethyl amines from p -QMs through the base- or Lewis acid-mediated or catalyzed vinylogous conjugate addition of amines and amides. − …”

Section: Introductionmentioning

confidence: 99%

“…the aryl migration of azides,56 desulfonylative amination, 57 etc. A few other protocols have also been reported for the preparation of diarylmethyl amines from p-…”

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confidence: 99%

Tropylium Salt-Promoted Vinylogous Aza-Michael Addition of Carbamates to para-Quinone Methides: Elaboration to Diastereomerically Pure α,α′-Diarylmethyl Carbamates

et al. 2021

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Carbocation catalysis is emerging as an important subarea of Lewis acid catalysis. Some stable and isolable carbocations have been successfully utilized as Lewis acid catalysts and promoters in many synthetic transformations. In this manuscript, we report a tropylium cation-promoted vinylogous aza-Michael addition of carbamates to para-quinone methides (QMs) to access a wide range of unsymmetrical α,α′-diarylmethyl carbamates. This mild protocol was effective for the vinylogous conjugate addition of (−)-menthyl carbamate to p-QMs, and the respective diastereomerically pure α,α′-diarylmethyl carbamate derivatives could be obtained in excellent yields and diastereoselectivities (up to >20:1 de).

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“…), NaOAc (1.0 equiv), toluene, 100 °C, 12 h.4.9. Synthesis of PhenanthridinePhenanthridines 269a,b were synthesized using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr-HCl (1,3-bis-(2,6-diisopropylphenyl)imidazolinium chloride) from 9-azidofluorenes 268,b via 1,2-aryl migration (Scheme 106)[84].…”

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confidence: 99%

Azides in the Synthesis of Various Heterocycles

et al. 2022

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In this review, we focus on some interesting and recent examples of various applications of organic azides such as their intermolecular or intramolecular, under thermal, catalyzed, or noncatalyzed reaction conditions. The aforementioned reactions in the aim to prepare basic five-, six-, organometallic heterocyclic-membered systems and/or their fused analogs. This review article also provides a report on the developed methods describing the synthesis of various heterocycles from organic azides, especially those reported in recent papers (till 2020). At the outset, this review groups the synthetic methods of organic azides into different categories. Secondly, the review deals with the functionality of the azido group in chemical reactions. This is followed by a major section on the following: (1) the synthetic tools of various heterocycles from the corresponding organic azides by one-pot domino reaction; (2) the utility of the chosen catalysts in the chemoselectivity favoring C−H and C-N bonds; (3) one-pot procedures (i.e., Ugi four-component reaction); (4) nucleophilic addition, such as Aza-Michael addition; (5) cycloaddition reactions, such as [3+2] cycloaddition; (6) mixed addition/cyclization/oxygen; and (7) insertion reaction of C-H amination. The review also includes the synthetic procedures of fused heterocycles, such as quinazoline derivatives and organometal heterocycles (i.e., phosphorus-, boron- and aluminum-containing heterocycles). Due to many references that have dealt with the reactions of azides in heterocyclic synthesis (currently more than 32,000), we selected according to generality and timeliness. This is considered a recent review that focuses on selected interesting examples of various heterocycles from the mechanistic aspects of organic azides.

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Iron-catalysed 1,2-aryl migration of tertiary azides

Abstract: 1,2-Aryl migration of α,α-diaryl tertiary azides was achieved by using the catalytic system of FeCl2/N-heterocyclic carbene (NHC) SIPr HCl. The reaction generated aniline products in good yields after one-pot reduction...

Cited by 11 publications

References 55 publications

Fluorine-Assisted Rearrangement of Geminal Azidofluorides to Imidoyl Fluorides

Fluorine-Assisted Rearrangement of Geminal Azidofluorides to Imidoyl Fluorides

Tropylium Salt-Promoted Vinylogous Aza-Michael Addition of Carbamates to para-Quinone Methides: Elaboration to Diastereomerically Pure α,α′-Diarylmethyl Carbamates

Azides in the Synthesis of Various Heterocycles

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