Chemo‐ and Enantioselective Intramolecular Silver‐Catalyzed Aziridinations

Ju, Minsoo; Weatherly, Cale D.; Guzei, Ilia A.; Schomaker, Jennifer M.

doi:10.1002/ange.201704786

Cited by 10 publications

(3 citation statements)

References 69 publications

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“…Noble metal such as rhodium [20][21][22], silver [23][24][25], ruthenium [26,27], palladium [28,29] and base metal such as iron [30][31][32], cobalt [33,34], copper [35,36] have been shown to accomplish C(sp 3 )-H aminations. Both of them, however, have some drawbacks in either reactivity or chemoselectivity for such catalysis.…”

Section: Introductionmentioning

confidence: 99%

Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C–H Amination vs. C=C Aziridination

Wang

Zheng

et al. 2020

Catalysts

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The reactivity, mechanism and chemoselectivity of the Mn-catalyzed intramolecular C–H amination versus C=C aziridination of allylic substrate cis-4-hexenylsulfamate are investigated by BP86 density functional theory computations. Emphasis is placed on the origins of high reactivity and high chemoselectivity of Mn catalysis. The N p orbital character of frontier orbitals, a strong electron-withdrawing porphyrazine ligand and a poor π backbonding of high-valent MnIII metal to N atom lead to high electrophilic reactivity of Mn-nitrene. The calculated energy barrier of C–H amination is 9.9 kcal/mol lower than that of C=C aziridination, which indicates that Mn-based catalysis has an excellent level of chemoselectivity towards C–H amination, well consistent with the experimental the product ratio of amintion-to-aziridination I:A (i.e., (Insertion):(Aziridination)) >20:1. This extraordinary chemoselectivity towards C–H amination originates from the structural features of porphyrazine: a rigid ligand with the big π-conjugated bond. Electron-donating substituents can further increase Mn-catalyzed C–H amination reactivity. The controlling factors found in this work may be considered as design elements for an economical and environmentally friendly C–H amination system with high reactivity and high chemoselectivity.

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Section: Introductionmentioning

confidence: 99%

Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C–H Amination vs. C=C Aziridination

Wang

Zheng

et al. 2020

Catalysts

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“…The strategy, if successful, would deliver 1,3-oxazinan-2-ones having substituent patterns different from those obtained in Zhang’s and Schomaker’s protocols. 12 13 Herein, we describe our findings of this study.…”

Section: Table 1 Screening Of Reaction Conditions For T...mentioning

confidence: 86%

“…12 The Schomaker group in 2017 disclosed the S N 2 reaction of [4.1.0]-carbamate-tethered aziridines towards the synthesis of 4-substituted 1,3-oxazinan-2-ones (Scheme 1 D). 13 We recently conducted intramolecular cyclization of N -Boc- N -(oxiran-2-ylmethyl)anilines (Scheme 1 E). 14 We observed that the reaction was completely regioselective in favor of 5- exo ring-closure, providing the corresponding 1,3-oxazolidin-2-ones when the distal epoxide substituent is an alkyl group.…”

Section: Table 1 Screening Of Reaction Conditions For T...mentioning

confidence: 99%

Trifluoroethanol-Mediated Cyclization of Two-Carbon-Tethered Epoxide–N-Boc Pairs: Completely Regioselective Synthesis of 3,6-Disubstituted 1,3-Oxazinan-2-ones

Das¹,

Chouhan²,

Borgohain³

et al. 2023

Synthesis

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The regio- and diastereoselective construction of biologically relevant cyclic carbamates under operationally simple and mild transition metal-free is challenging and has led to a demand for efficient methods for their synthesis. The intramolecular ring-opening cyclization of N-Boc-tethered epoxides leading to the formation of cyclic carbamates is equipped with many favorable synthetic features, including easy accessibility of starting materials in a stereodefined form, high diversification points in the substrates, and favorable entropy factor. However, its use in the construction of 1,3-oxazinan-2-ones remains largely neglected. Specifically, prior to 2020, only few 1,3-oxazinan-2-ones were successfully synthesized using this strategy. Moreover, our very own recent attempt to access these heterocycles using one-carbon-tethered N-Boc/epoxide pairs was met with a little success as the process furnished either only 1,3-oxazolidin-2-ones or nearly equal amounts of 1,3-oxazolidin-2-ones and 1,3-oxazinan-2-ones. Herein, we demonstrate that when the epoxide and N-Boc moieties are connected by a two-carbon tether, the cyclization could deliver 1,3-oxazinan-2-ones containing vicinal stereocenters, as sole regio- and diastereomers in high yields (up to 95% yield), irrespective of whether the distal epoxide substituent is alkyl or aryl, or the epoxide is cis- or trans-configured.

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Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

et al. 2022

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This review outlines the progress over recent years in the reactions involving combined approach of hypervalent iodine reagents and transition metals such as palladium, nickel, iridium, gold, rhodium, copper, iron, ruthenium, platinum, silver, zinc, rhenium and cobalt. This approach enables organic transformations complimentary to traditional manifolds. Hypervalent iodine reagents play a preeminent role in organic chemistry due to their versatile reactivity, heteroatom ligands and mild reaction conditions. These reagents in combination of transition metal compounds are used in many synthetically useful organic reactions such as oxidation, rearrangement, amination, halogenation, amidation, ring-opening, cyclization and CÀ H and CÀ C functionalization reactions, etc. which are discussed here. Combination with Cobalt 2.3. Reactions of Hypervalent Iodine Reagents with Copper 2.4. Reactions of Hypervalent Iodine Reagents in Combination with Nickel 2.5. Reactions of Hypervalent Iodine Reagents in Combination with Zinc 3. Transformations Involving Hypervalent Iodine Reagents and 2 nd Transition Series Metals 3.1. Reactions of Hypervalent Iodine Reagents in Combination with Ruthenium 3.2. Reactions of Hypervalent Iodine Reagents in Combination With Rhodium 3.3. Reactions of Hypervalent Iodine Reagent in Combination With Palladium 3.4. Reactions of Hypervalent Iodine Reagents in Combination with Silver 4. Transformations Involving Hypervalent Iodine Reagents and 3rd Transition Series Metals 4.1. Reactions of Hypervalent Iodine Reagents in Combination with Rhenium 4.2. Reactions of Hypervalent Iodine Reagents in Combination with Iridium 4.3. Reactions of Hypervalent Iodine Reagents in Combination with Platinum 4.4. Reactions of Hypervalent Iodine Reagents in Combination with Gold 5. Conclusion

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Chemo‐ and Enantioselective Intramolecular Silver‐Catalyzed Aziridinations

Cited by 10 publications

References 69 publications

Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C–H Amination vs. C=C Aziridination

Mechanism and Chemoselectivity of Mn-Catalyzed Intramolecular Nitrene Transfer Reaction: C–H Amination vs. C=C Aziridination

Trifluoroethanol-Mediated Cyclization of Two-Carbon-Tethered Epoxide–N-Boc Pairs: Completely Regioselective Synthesis of 3,6-Disubstituted 1,3-Oxazinan-2-ones

Combined Approach of Hypervalent Iodine Reagents and Transition Metals in Organic Reactions

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