Divergent and Chemoselective Transformations of Thioamides with Designed Carbene Equivalents

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...

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Published inChemistry : a European journal Vol. 25; no. 44; pp. 10314 - 10318
Main Authors Saito, Masato, Kobayashi, Yusuke, Takemoto, Yoshiji
Format Journal Article
LanguageEnglish
Published WEINHEIM Wiley 06.08.2019
Wiley Subscription Services, Inc
Subjects
Aqueous solutions
Chemical compounds
Chemical reactions
Chemistry
Chemistry, Multidisciplinary
chemoselectivity
Coupling (molecular)
Drugs
enaminones
halogen bonding
hypervalent compounds
Peptides
Physical Sciences
Prodrugs
Science & Technology
Steroid hormones
Steroids
Thiazoles
chemoselectivity
SUBSTITUTION
ACTIVATION
thiazoles
hypervalent compounds
PHENYLIODONIUM YLIDE
STABILITY
REACTIVITY
HALOGEN
enaminones
BETA-SHEET
IODONIUM YLIDES
ESTERS
halogen bonding
HYPERVALENT IODINE REAGENTS
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Summary: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. Useful carbene equivalents: The reactions of thioamides with ortho‐nitro‐substituted iodonium ylides proceeded under mild conditions to give enaminones or thiazoles. This protocol allowed the use of protic solvents, including aqueous solutions, and therefore coupling reactions with complex molecules were possible. A mild and efficient method for the synthesis of various iodonium ylides was also established (see scheme).
Bibliography:ObjectType-Article-1
SourceType-Scholarly Journals-1
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ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201902699