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Divergent and Chemoselective Transformations of Thioamides with Designed Carbene Equivalents
Author(s) -
Saito Masato,
Kobayashi Yusuke,
Takemoto Yoshiji
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902699
Subject(s) - thioamide , ylide , carbene , chemistry , prodrug , conjugated system , halogen , combinatorial chemistry , molecule , aqueous solution , chemoselectivity , nitro , coupling reaction , organic chemistry , catalysis , biochemistry , alkyl , polymer
Abstract The reactions of thioamides with ortho ‐nitro‐substituted iodonium ylides proceeded under mild conditions to give enaminones or thiazoles, depending on the iodonium ylide used. This protocol allowed the use of protic solvents, including aqueous solutions, and therefore coupling reactions with complex molecules such as peptides or steroids were possible. A mild and efficient method for the synthesis of various iodonium ylides was established. DFT calculations suggested that the halogen bonding between a thioamide and iodonium ylide was important in this chemoselective coupling reaction. The potential use of enaminones conjugated with pharmaceuticals as prodrugs was also demonstrated.