Mechanistic Pathways in Amide Activation: Flexible Synthesis of Oxazoles and Imidazoles

Giovanni Di Mauro; Boris Maryasin; Daniel Kaiser; Saad Shaaban; Leticia Gonzalez; Nuno Maulide

doi:10.1021/acs.orglett.7b01678

Mechanistic Pathways in Amide Activation: Flexible Synthesis of Oxazoles and Imidazoles

Giovanni Di Mauro, Boris Maryasin, Daniel Kaiser, Saad Shaaban, Leticia Gonzalez, Nuno Maulide (Corresponding author)

Publications: Contribution to journal › Article › Peer Reviewed

Abstract

The preparation of substituted aminooxazoles and aminoimidazoles from α-arylamides and α-aminoamides through triflic anhydride-mediated amide activation is reported. These reactions proceed via the intermediacy of nitrilium adducts and feature N-oxide-promoted umpolung of the α-position of amides as well as a mechanistically intriguing sequence that results in sulfonyl migration from nitrogen to carbon. Quantum-chemical mechanistic analysis sheds light on the intricacies of the process.

Original language	English
Pages (from-to)	3815-3818
Number of pages	4
Journal	Organic Letters
Volume	19
Issue number	14
DOIs	https://doi.org/10.1021/acs.orglett.7b01678
Publication status	Published - 21 Jul 2017

Austrian Fields of Science 2012

104015 Organic chemistry

Keywords

FORMAL 3+2 CYCLOADDITION
METAL-FREE SYNTHESIS
OXO GOLD CARBENES
SECONDARY AMIDES
TRIFLIC ANHYDRIDE
ELECTROPHILIC REARRANGEMENTS
CHEMOSELECTIVE SYNTHESIS
RECEPTOR ANTAGONISTS
THIAZOLE ALKALOIDS
ALKYNE OXIDATION

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title = "Mechanistic Pathways in Amide Activation: Flexible Synthesis of Oxazoles and Imidazoles",

abstract = "The preparation of substituted aminooxazoles and aminoimidazoles from α-arylamides and α-aminoamides through triflic anhydride-mediated amide activation is reported. These reactions proceed via the intermediacy of nitrilium adducts and feature N-oxide-promoted umpolung of the α-position of amides as well as a mechanistically intriguing sequence that results in sulfonyl migration from nitrogen to carbon. Quantum-chemical mechanistic analysis sheds light on the intricacies of the process.",

keywords = "FORMAL 3+2 CYCLOADDITION, METAL-FREE SYNTHESIS, OXO GOLD CARBENES, SECONDARY AMIDES, TRIFLIC ANHYDRIDE, ELECTROPHILIC REARRANGEMENTS, CHEMOSELECTIVE SYNTHESIS, RECEPTOR ANTAGONISTS, THIAZOLE ALKALOIDS, ALKYNE OXIDATION",

author = "{Di Mauro}, Giovanni and Boris Maryasin and Daniel Kaiser and Saad Shaaban and Leticia Gonzalez and Nuno Maulide",

note = "Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

month = jul,

day = "21",

doi = "10.1021/acs.orglett.7b01678",

language = "English",

volume = "19",

pages = "3815--3818",

journal = "Organic Letters",

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T1 - Mechanistic Pathways in Amide Activation: Flexible Synthesis of Oxazoles and Imidazoles

AU - Di Mauro, Giovanni

AU - Maryasin, Boris

AU - Kaiser, Daniel

AU - Shaaban, Saad

AU - Gonzalez, Leticia

AU - Maulide, Nuno

PY - 2017/7/21

Y1 - 2017/7/21

N2 - The preparation of substituted aminooxazoles and aminoimidazoles from α-arylamides and α-aminoamides through triflic anhydride-mediated amide activation is reported. These reactions proceed via the intermediacy of nitrilium adducts and feature N-oxide-promoted umpolung of the α-position of amides as well as a mechanistically intriguing sequence that results in sulfonyl migration from nitrogen to carbon. Quantum-chemical mechanistic analysis sheds light on the intricacies of the process.

AB - The preparation of substituted aminooxazoles and aminoimidazoles from α-arylamides and α-aminoamides through triflic anhydride-mediated amide activation is reported. These reactions proceed via the intermediacy of nitrilium adducts and feature N-oxide-promoted umpolung of the α-position of amides as well as a mechanistically intriguing sequence that results in sulfonyl migration from nitrogen to carbon. Quantum-chemical mechanistic analysis sheds light on the intricacies of the process.

KW - FORMAL 3+2 CYCLOADDITION

KW - METAL-FREE SYNTHESIS

KW - OXO GOLD CARBENES

KW - SECONDARY AMIDES

KW - TRIFLIC ANHYDRIDE

KW - ELECTROPHILIC REARRANGEMENTS

KW - CHEMOSELECTIVE SYNTHESIS

KW - RECEPTOR ANTAGONISTS

KW - THIAZOLE ALKALOIDS

KW - ALKYNE OXIDATION

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U2 - 10.1021/acs.orglett.7b01678

DO - 10.1021/acs.orglett.7b01678

M3 - Article

SN - 1523-7060

VL - 19

SP - 3815

EP - 3818

JO - Organic Letters

JF - Organic Letters

IS - 14

ER -

Mechanistic Pathways in Amide Activation: Flexible Synthesis of Oxazoles and Imidazoles

Abstract

Austrian Fields of Science 2012

Keywords

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