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Chemistry

University of Richmond

Series

Silyl triflates

Publication Year

Articles 1 - 4 of 4

Full-Text Articles in Physical Sciences and Mathematics

One-Pot Enol Silane Formation-Allylation Of Ketones Promoted By Trimethylsilyl Trifluoromethanesulfonate, Elizabeth D. Heafner, Xuechun Lin, Alexa Connors, Hanyu Zhong, R. J. Coyle, Yiqi Liu, C. Wade Downey Jan 2023

One-Pot Enol Silane Formation-Allylation Of Ketones Promoted By Trimethylsilyl Trifluoromethanesulfonate, Elizabeth D. Heafner, Xuechun Lin, Alexa Connors, Hanyu Zhong, R. J. Coyle, Yiqi Liu, C. Wade Downey

Chemistry Faculty Publications

Ketones and related substrate classes undergo enol silane formation in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) and triethylamine, reaction conditions that also promote the in situ ionization of allyl propionates. When these two processes are performed in one pot, allylation of the ketone is observed in high yields. Aldehydes, esters, and thioesters also serve as enol silane precursors under these conditions. When unsymmetrical allyl cations are employed, regioselectivity depends upon the electronic and steric properties of the substituents.


Silyl Trifluoromethanesulfonate-Activated Para-Methoxybenzyl Methyl Ether As An Alkylating Agent For Thiols And Aryl Ketones, C. Wade Downey, Sarah E. Covington, Derek C. Obenschain, Evan Halliday, James T. Rague, Danielle N. Confair Sep 2014

Silyl Trifluoromethanesulfonate-Activated Para-Methoxybenzyl Methyl Ether As An Alkylating Agent For Thiols And Aryl Ketones, C. Wade Downey, Sarah E. Covington, Derek C. Obenschain, Evan Halliday, James T. Rague, Danielle N. Confair

Chemistry Faculty Publications

para-Methoxybenzyl methyl ether acts as an alkylating agent for thiols in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine base in good yields (58-96%). Aryl ketones are alkylated under similar conditions, probably through an enol silane intermediate, also in high yields (67-95%). The active alkylating species is likely a p-methoxybenzyl cation.


Silyl Triflate-Accelerated Additions Of Catalytically Generated Zinc Acetylides To N-Phenyl Nitrones, C. Wade Downey, Erin N. Maxwell, Danielle N. Confair Aug 2014

Silyl Triflate-Accelerated Additions Of Catalytically Generated Zinc Acetylides To N-Phenyl Nitrones, C. Wade Downey, Erin N. Maxwell, Danielle N. Confair

Chemistry Faculty Publications

Terminal alkynes readily form zinc acetylides in the presence of iPr2NEt and 20 mol% ZnBr2, then attack N-phenyl nitrones activated by trimethylsilyl trifluoromethanesulfonate. Deprotection with aqueous acid yields the N-hydroxyl propargylamine. Yields are generally high for nitrones derived from aromatic aldehydes. Control experiments suggest that the silyl triflate has a significant accelerating effect upon the reaction.


One-Pot Enol Silane Formation-Mukaiyama–Mannich Addition Of Ketones, Amides, And Thioesters To Nitrones In The Presence Of Trialkylsilyl Trifluoromethanesulfonates, C. Wade Downey, Carolyn M. Dombrowski, Erin N. Maxwell, Chelsea L. Safran, Odamea A. Akomah Sep 2013

One-Pot Enol Silane Formation-Mukaiyama–Mannich Addition Of Ketones, Amides, And Thioesters To Nitrones In The Presence Of Trialkylsilyl Trifluoromethanesulfonates, C. Wade Downey, Carolyn M. Dombrowski, Erin N. Maxwell, Chelsea L. Safran, Odamea A. Akomah

Chemistry Faculty Publications

Ketones, amides, and thioesters form enol silanes and add to N-phenylnitrones in one pot in the presence of trimethylsilyl trifluoromethanesulfonate and trialkylamine. The reaction is general to a range of silyl trifluoromethanesulfonates and N-phenylnitrones. The b-(silyloxy)amino carbonyl products are stable to chromatography and can be isolated in 63-99% yield.