Design and synthesis of Fmoc-SPPS-ready iodoarene amino acid pre-catalysts and their reactivity in the catalytic oxytosylation of ketones

Lex, Timothy R.; Swasy, Maria I.; Panda, Soham; Brummel, Beau R.; Giambalvo, Lauren N.; Gross, Kristopher G.; McMillen, Colin D.; Kobra, Khadijatul; Pennington, William T.; Whitehead, Daniel C.

doi:10.1016/j.tetlet.2020.151723

“…The data that support the findings of this study are available in the Supporting Information of this article. The authors have cited additional references within the Supporting Information [26–33] …”

Section: Methodsmentioning

confidence: 99%

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Zogu,

Ullah,

Spanopoulos

et al. 2024

Angewandte Chemie

0

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Sulfur(VI) Fluoride Exchange (SuFEx) chemistry stands as a well‐established method for swiftly constructing complex molecules in a modular fashion. An especially promising segment of this toolbox is reserved for multidimensional SuFEx hubs: three or more substituents pluggable into a singular SVI centre to make ‘beyondlinear’ clicked constructions. Sulfurimidoyl difluorides (RNSOF2) stand out as the prime example of this, however their preparation from the scarcely available thionyl tetrafluoride (SOF4) limits this chemistry to only a few laboratories with access to this gas. In this work, we identify silver pentafluorooxosulfate (AgOSF5) as a viable SuFEx hub with reactivity equal to SOF4. The AgF2‐mediated oxidation of SOCl2 gives rise to the hexacoordinate AgOSF5 adduct, which in contact with primary amines produces the sulfurimidoyl fluorides in high yields. In addition, we have found this workflow to be fully extendable to the trifluoromethyl homologue, AgOSF4CF3, and we propose the use of AgOSF4X salts as a general route to azasulfur SuFEx electrophiles from commercial starting materials.

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“…Notably, there was no asymmetric induction observed during these reactions. 153 In the continuation of searching for high selectivities during these reactions, a novel C 2 -symmetric chiral iodoarene 236 was synthesised and used as precatalyst to transfer the chirality in the presence of terminal oxidant during the a-oxytosylation of acetyl enol ether 232. 154 Once again, the catalytic reaction was found slower than the stoichiometric reaction, but the aoxytosylated product 233 was obtained as (S)-isomer in 90% ee (Scheme 66).…”

Section: A-functionalisations Of Ketonesmentioning

confidence: 99%

Progress in organocatalysis with hypervalent iodine catalysts

Singh

¹

,

Shetgaonkar

²

,

Krishnan

³

et al. 2022

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Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Zogu,

Ullah,

Spanopoulos

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

Sulfur(VI) Fluoride Exchange (SuFEx) chemistry stands as a well‐established method for swiftly constructing complex molecules in a modular fashion. An especially promising segment of this toolbox is reserved for multidimensional SuFEx hubs: three or more substituents pluggable into a singular SVI centre to make ‘beyondlinear’ clicked constructions. Sulfurimidoyl difluorides (RNSOF2) stand out as the prime example of this, however their preparation from the scarcely available thionyl tetrafluoride (SOF4) limits this chemistry to only a few laboratories with access to this gas. In this work, we identify silver pentafluorooxosulfate (AgOSF5) as a viable SuFEx hub with reactivity equal to SOF4. The AgF2‐mediated oxidation of SOCl2 gives rise to the hexacoordinate AgOSF5 adduct, which in contact with primary amines produces the sulfurimidoyl fluorides in high yields. In addition, we have found this workflow to be fully extendable to the trifluoromethyl homologue, AgOSF4CF3, and we propose the use of AgOSF4X salts as a general route to azasulfur SuFEx electrophiles from commercial starting materials.

show abstract

Design and synthesis of Fmoc-SPPS-ready iodoarene amino acid pre-catalysts and their reactivity in the catalytic oxytosylation of ketones

Cited by 4 publications

References 18 publications

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Progress in organocatalysis with hypervalent iodine catalysts

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

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Design and synthesis of Fmoc-SPPS-ready iodoarene amino acid pre-catalysts and their reactivity in the catalytic oxytosylation of ketones

Cited by 4 publications

References 18 publications

Perfluorooxosulfate Salts as SOF4‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Perfluorooxosulfate Salts as SOF4‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Progress in organocatalysis with hypervalent iodine catalysts

Perfluorooxosulfate Salts as SOF4‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Contact Info

Product

Resources

About

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

Perfluorooxosulfate Salts as SOF₄‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles