Intramolecular PhIO Mediated Copper-Catalyzed Aziridination of Unsaturated Sulfamates: A New Direct Access to Polysubstituted Amines from Simple Homoallylic Alcohols

Durán, Fernando Javier; Leman, Loïc; Ghini, Alberto A.; Burton, Gerardo; Dauban, Philippe; Dodd, Robert H.

doi:10.1021/ol0200899

Cited by 123 publications

(55 citation statements)

References 33 publications

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“…Such findings would be of value, given the unique reactivity and potential utility of the isolable bicyclic aziridines. Accordingly, these compounds react as electrophiles with alcohols, carboxylates, thiols, amines, N 3 -, and CN -to generate seven-membered [1,2,3]oxathiazepane-2,2-dioxides [96]. In one rather remarkable example, displacement at a tetrasubstituted c-center occurs stereospecifically and in preference to attack at the less hindered d-site (Scheme 17.28) [74].…”

Section: Sulfamate Estersmentioning

confidence: 99%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

104

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17 Rhodium(II)-Catalyzed Oxidative Amination 380 Scheme 17.1 Copper-catalyzed decomposition of arylsulfonyl azides. Scheme 17.2 Intramolecular C-H amination of an iminoiodinane. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 381 Scheme 17.3 Metal porphyrin-catalyzed allylic amination. Scheme 17.4 C-H amination by a radical-rebound mechanism. 17 Rhodium(II)-Catalyzed Oxidative Amination 382 Scheme 17.5 Rhodium-catalyzed N-atom transfer using NsN=IPh. Scheme 17.6 Stereospecific C-H amination under rhodium-catalyzed conditions. 17.3 Intermolecular C-H Amination with Rhodium(II) Catalysts 383 Scheme 17.7 Radical clock study of metallo-nitrene C-H insertion. Scheme 17.8 Intermolecular C-H insertion by chiral rhodium catalysts. 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 385 Scheme 17.11 Allylic and benzylic amination using PhI(OAc) 2 . 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 387 Tab. 17.1 C-H amination of 18 carbamate esters. Entry Substrate Product Entry Substrate Product 17.5 Intramolecular C-H Amination with Rhodium(II) Catalysts 389 Scheme 17.14 Ketone formation by 28 alcohol-derived carbamates. 17.7 Enantioselective C-H Insertion with Sulfamate Esters 401 Scheme 17.29 Oxidative cyclization of unsaturated sulfonamides. Scheme 17.30 Preliminary investigations of asymmetric C-H amination. 17.11 Applications of C-H Amination in Synthesis 407 17.11 Applications of C-H Amination in Synthesis 409 Scheme 17.39 Asymmetric synthesis of (-)-tetrodotoxin. 17 Rhodium(II)-Catalyzed Oxidative Amination 410 Scheme 17.40 Nucleophilic ring opening of N-acylated oxathiazinanes. Scheme 17.41 Nickel-catalyzed cross-coupling of phenol-derived sulfamate esters.

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Section: Sulfamate Estersmentioning

confidence: 99%

Rhodium(II)‐Catalyzed Oxidative Amination

Espino

Bois

2005

Modern Rhodium‐Catalyzed Organic Reactions

104

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“…Recently, the groups of Du Bois and Che have independently reported that the formation of aryliodinanes and the insertion of metallonitrenoids into C=C or CÀH bonds can be conducted with a one-pot procedure. [8][9][10][11] This methodology has been successfully used for the synthesis of natural aminoglycoside frameworks. For example, Rojas showed the use of copper and rhodium catalysts in amidoglycosylation reactions of d-allal-derived carbamates to furnish 2-aminoglycosylated products.…”

Section: Introductionmentioning

confidence: 99%

Stereocontrolled Intramolecular Aziridination of Glycals: Ready Access to Aminoglycosides and Mechanistic Insights from DFT Studies

Lorpitthaya

Xie

Kuo

et al. 2008

Chemistry A European J

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Stereocontrolled intramolecular aziridination of the glycal-derived sulfamates offers a highly efficient strategy to divergently prepare aminoglycosides. Rhodium-catalyzed nitrogen-atom transfer to C==C bonds formed semistable aziridines, which were subjected to various nucleophiles (C, O, S, and N) to give cyclic sulfamate-containing aminosugar derivatives selectively. The second nucleophilic displacement of sulfonyloxy moieties of [1,2,3]-oxathiazepane-2,2- dioxides allows straightforward access to aminoglycosides with selective alpha- or beta-linkages. This approach is operationally simple, complements existing methods, and is a versatile protocol for the synthesis of polyfunctionalized amino sugars. In addition, the mechanism of the rhodium-catalyzed intramolecular aziridination of glycals and its ring-opening reaction was extensively studied by using DFT calculations.

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“…With v-butenyl sulfonamide 29a, an intramolecular process can ensue to provide the bicyclic aziridine in good yield (Scheme 2.7). These and other investigations have shown the process to be stereospecific (Table 2.4, entry 2), whereby alkene geometry is preserved in the product [68]. Moreover, existing chiral centers can impose diastereoselectivity, as shown by the intramolecular aziridination of alkenyl sulfonamide 29c, which proceeds with a 10 : 1 syn : anti ratio [69].…”

Section: Aziridines J17mentioning

confidence: 78%

Three‐Membered Heterocycles. Structure and Reactivity

Murphree

2011

Modern Heterocyclic Chemistry

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Intramolecular PhIO Mediated Copper-Catalyzed Aziridination of Unsaturated Sulfamates: A New Direct Access to Polysubstituted Amines from Simple Homoallylic Alcohols

Cited by 123 publications

References 33 publications

Rhodium(II)‐Catalyzed Oxidative Amination

Rhodium(II)‐Catalyzed Oxidative Amination

Stereocontrolled Intramolecular Aziridination of Glycals: Ready Access to Aminoglycosides and Mechanistic Insights from DFT Studies

Three‐Membered Heterocycles. Structure and Reactivity

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