Cardiff University | Prifysgol Caerdydd ORCA
Online Research @ Cardiff 
WelshClear Cookie - decide language by browser settings

General hydroamination of allenamides: mechanistic Insights with an acetate adduct and 1,1,1,3,3,3-hexafluoro-2-propanol

Sagar, Kadiyala, Pradhan, Tapas R. ORCID: https://orcid.org/0000-0003-1480-7799, Farah, Abdikani Omar, Wise, Henry R., Merja, Bhailal C., Srimannarayana, Malempati, Cheong, Paul Ha-Yeon and Park, Jin Kyoon 2023. General hydroamination of allenamides: mechanistic Insights with an acetate adduct and 1,1,1,3,3,3-hexafluoro-2-propanol. Organic Letters 25 (30) , pp. 553-5702. 10.1021/acs.orglett.3c01820

Full text not available from this repository.

Abstract

The 1,1,1,3,3,3-hexafluoro-2-propanol-assisted allenamide activation enables metal-free regioselective intermolecular interception of amines, constituting a general C–N bond formation process for accessing value-added 1,3-diamines. Exclusive N-chemoselectivity (vs C for anilines) and regioselectivity were achieved for a broad range of substrates. Late-stage modification and further transformations of the 1,3-diamine products showcased the practicability and benefits of this strategy. Experimental mechanistic studies revealed that 1,1,1,3,3,3-hexafluoro-2-propanol mediates the proton transfer for activation of the allenamide. Density functional theory computations revealed the role of NaOAc in the formation of the reactive electrophilic intermediate, which ultimately governs the selective formation of the 1,3-diamine product.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: American Chemical Society
ISSN: 1523-7060
Date of Acceptance: 25 July 2023
Last Modified: 16 May 2024 01:39
URI: https://orca.cardiff.ac.uk/id/eprint/165570

Actions (repository staff only)

Edit Item Edit Item