Synthesis of Imide and Amine Derivatives via Deoxyamination of Alcohols Using N‐Haloimides and Triphenylphosphine

• Published in: ChemistrySelect (Weinheim) Vol. 6; no. 33; pp. 8874 - 8878
• Main Authors: Irving, Charles D., Floreancig, Jack T., Gasonoo, Makafui, Kelley, Alexandra S., Laulhé, Sébastien
• Format: Journal Article
• Language: English
• Published: Germany 07-09-2021
• Subjects: Amine Precursors; Deoxyamination; Mitsunobu Reaction; N-haloimides; Triphenylphosphine; Amine Precursors; N-haloimides; Mitsunobu Reaction; Triphenylphosphine; Deoxyamination
• ISSN: 2365-6549; 2365-6549
• DOI: 10.1002/slct.202102296

A deoxyamination methodology of activated and unactivated alcohols is presented. The reaction is mediated by phosphonium intermediates generated in situ from N‐haloimides and triphenylphosphine. The protocol allows for the synthesis of phthalimide and amine derivatives in moderate to good yields at room temperature. A series of NMR experiments have provided insight into the reactive intermediates involved and the mechanism of this deoxyamination reaction.
Two deoxyamination methodologies of alcohols are presented. These reactions are mediated by phosphonium species generated in situ through the reaction of triphenylphosphine and N‐haloimides. When the reaction is performed in presence of Cs2CO3 as a base additive, the alcohol is transformed into the imide product, thereby emulating a Mitsunobu reaction without the need of azodicarboxylate activating agent. If external amine source is added, the alcohol is transformed into the secondary or tertiary amine product.