Ring Opening of Aziridines by Pendant Sulfamates Allows for Regioselective and Stereospecific Preparation of Vicinal Diamines

Nagamalla, Someshwar; Thomas, Annu Anna; Nirpal, Appasaheb K.; Mague, Joel T.; Sathyamoorthi, Shyam

doi:10.1021/acs.joc.3c01731

Cited by 6 publications

(4 citation statements)

References 64 publications

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“…This outcome complements existing aziridination protocols, where protection of oxidatively sensitive groups is not required due to the anaerobic nature of our protocol. 37,38,39 Notably, in all cases, allylic C-H amination products were not detected, illustrating that this aziridination approach is highly chemoselective.…”

mentioning

confidence: 86%

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Mitchell,

Hussain,

Bansode

et al. 2024

Preprint

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Herein, we report that readily accessible azoxy-triazenes can serve as nitrogen atom sources under visible light excitation for the phthalimido-protected aziridination of alkenes. This approach eliminates the need for external oxidants, precious transition metals, and photocatalysts, marking a departure from conventional methods. The versatility of this transformation extends to the selective aziridination of both activated and unactivated multi-substituted alkenes of varying electronic profiles. Notably, this process avoids the formation of competing C–H insertion products. The described protocol is operationally simple, scalable, and adaptable to photoflow conditions. Mechanistic studies support that the photofragmentation of azoxy-triazenes results in the generation of a free singlet nitrene. Furthermore, a mild photoredox-catalyzed N–N cleavage of the protecting group to furnish the free aziridines is reported. Our findings contribute to the advancement of sustainable and practical methodologies for the synthesis of nitrogen-containing compounds, showcasing the potential for broader applications in synthetic chemistry.

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mentioning

confidence: 86%

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Mitchell,

Hussain,

Bansode

et al. 2024

Preprint

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“…These reactions provided a variety of vicinal diamine products. [21] I was particularly impressed by Someshwar's conversion of these products into an array of interesting heterocycles.…”

Section: Intramolecular Ring-opening Reactions Of Epoxides and Azirid...mentioning

confidence: 99%

“…Someshwar, Annu, and Dr. Appasaheb Nirpal used these reaction conditions to explore analogous ring‐openings of aziridines (Scheme 9). These reactions provided a variety of vicinal diamine products [21] . I was particularly impressed by Someshwar's conversion of these products into an array of interesting heterocycles.…”

Section: Intramolecular Ring‐opening Reactions Of Epoxides and Azirid...mentioning

confidence: 99%

Fun With Unusual Functional Groups: Sulfamates, Phosphoramidates, and Di‐tert‐butyl Silanols

Sathyamoorthi

2024

Eur J Org Chem

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Compared to ubiquitous functional groups such as alcohols, carboxylic acids, amines, and amides, which serve as central “actors” in most organic reactions, sulfamates, phosphoramidates, and (ditert‐butyl)silanols have historically been viewed as “extras”. Largely considered functional group curiosities rather than launch‐points of vital reactivity, the chemistry of these moieties is under‐developed. Our research program has uncovered new facets of reactivity of each of these functional groups, and we are optimistic that the chemistry of these fascinating molecules can be developed into truly general transformations, useful for chemists across multiple disciplines. In the ensuing sections, I will describe our efforts to develop new reactions with these “unusual” functional groups, namely sulfamates, phosphoramidates, and di‐tert‐butyl silanols.

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“…Finally, cholesterol ( 1bc ), with an unprotected alcohol, gave a moderate yield of 2bc . This outcome complements existing aziridination protocols, where protection of oxidatively sensitive groups is not required due to the anaerobic nature of our protocol. − Notably, in all cases, allylic C–H amination products were not detected, illustrating that this aziridination approach is highly chemoselective.…”

mentioning

confidence: 99%

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Mitchell,

Hussain,

Bansode

et al. 2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Herein, we report that readily accessible azoxy-triazenes can serve as nitrogen atom sources under visible light excitation for the phthalimido-protected aziridination of alkenes. This approach eliminates the need for external oxidants, precious transition metals, and photocatalysts, marking a departure from conventional methods. The versatility of this transformation extends to the selective aziridination of both activated and unactivated multisubstituted alkenes of varying electronic profiles. Notably, this process avoids the formation of competing C–H insertion products. The described protocol is operationally simple, scalable, and adaptable to photoflow conditions. Mechanistic studies support the idea that the photofragmentation of azoxy-triazenes results in the generation of a free singlet nitrene. Furthermore, a mild photoredox-catalyzed N–N cleavage of the protecting group to furnish the free aziridines is reported. Our findings contribute to the advancement of sustainable and practical methodologies for the synthesis of nitrogen-containing compounds, showcasing the potential for broader applications in synthetic chemistry.

show abstract

Ring Opening of Aziridines by Pendant Sulfamates Allows for Regioselective and Stereospecific Preparation of Vicinal Diamines

Cited by 6 publications

References 64 publications

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

Fun With Unusual Functional Groups: Sulfamates, Phosphoramidates, and Di‐tert‐butyl Silanols

Aziridination via Nitrogen-Atom Transfer to Olefins from Photoexcited Azoxy-Triazenes

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