Formation of Hindered Arylcarbamates using Alkyl Aryl Carbonates under Highly Reactive Conditions. Issue 13 (10th May 2017)

• Record Type: Journal Article
• Authors: Shahsavari, Shahien; Gooding, James; Wigstrom, Travis; Fang, Shiyue
• Is Part Of: ChemistrySelect. Volume 2:Issue 13(2017)
• Page Start: 3959
• Page End: 3963
• Publication Date: 2017-05-10
• Subjects: Amines -- carbamates -- carbamylation -- protecting groups -- synthetic methods; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.201700364
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: Hindered O ‐ tert ‐alkyl N ‐arylcarbamates were conveniently prepared by treating arylamines with aryl tert ‐alkyl carbonates in the presence of a strong base. The new method avoids the use of sensitive and difficult‐to‐access dialkyl dicarbonates and isocyanates, which are most commonly used in known methods. Instead, the stable and readily accessible alkyl aryl carbonates are used. Therefore, the new method is particularly suitable for the synthesis of N ‐arylcarbamates that contain a complex O ‐alkyl moiety. Using the method, electron‐rich and electron‐poor, and primary and secondary arylamines can all be conveniently converted to their carbamates with acceptable yields. The method was also found equally effective for the synthesis of the less hindered O ‐secondary and O ‐primary alkyl N ‐arylcarbamates. Abstract : Arylamines are directly converted to hindered carbamates using the stable and easily accessible alkyl aryl carbonates. Using this carbamylation method, converting the arylamines to isocyanate intermediates using toxic triphosgene or multistep preparation of sensitive di‐alkyl‐dicarbonate carbamylation agents, which are needed in the two mostly used methods, can be avoided.