Convenient Assembly of Privileged (Hetero)Arene-Fused Benzo[1.4]oxazepines via Two Tandem S N Ar Events. Part 1 – On the Importance of the Intermittent Smiles Rearrangement

Research output

1 Citation (Scopus)

Abstract

New bis-nucleophilic precursors to [1.4]oxazepines synthesized via S N Ar-Smiles rearrangement-S N Ar cascade have been designed. Employing them in base-promoted condensation with aromatic bis-electrophiles allowed differentiating between highly and poorly reactive substrates (i.e. those which can and cannot pass through the Smiles rearrangement barrier, respectively). The reactivity toward the desired course of cyclization can be restored by introducing electron-withdrawing substituents in the bis-electrophile precursor. This strongly argues for the importance of the Smiles rearrangement for the successful overall ring formation.

Original languageEnglish
JournalEuropean Journal of Organic Chemistry
DOIs
Publication statusE-pub ahead of print - 4 Apr 2019

Fingerprint

Oxazepines
Cyclization
Condensation
cascades
reactivity
condensation
assembly
Electrons
rings
Substrates
electrons

Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry

Cite this

@article{fb8346ae2d8644cca9e00221e3e86935,
title = "Convenient Assembly of Privileged (Hetero)Arene-Fused Benzo[1.4]oxazepines via Two Tandem S N Ar Events. Part 1 – On the Importance of the Intermittent Smiles Rearrangement",
abstract = "New bis-nucleophilic precursors to [1.4]oxazepines synthesized via S N Ar-Smiles rearrangement-S N Ar cascade have been designed. Employing them in base-promoted condensation with aromatic bis-electrophiles allowed differentiating between highly and poorly reactive substrates (i.e. those which can and cannot pass through the Smiles rearrangement barrier, respectively). The reactivity toward the desired course of cyclization can be restored by introducing electron-withdrawing substituents in the bis-electrophile precursor. This strongly argues for the importance of the Smiles rearrangement for the successful overall ring formation.",
keywords = "Nucleophilic aromatic substitution, Oxazepines, Privileged structures, Smiles rearrangement, Synthons",
author = "Alexander Sapegin and Mikhail Krasavin",
year = "2019",
month = "4",
day = "4",
doi = "10.1002/ejoc.201900263",
language = "English",
journal = "European Journal of Organic Chemistry",
issn = "1434-193X",
publisher = "Wiley-Blackwell",

}

TY - JOUR

T1 - Convenient Assembly of Privileged (Hetero)Arene-Fused Benzo[1.4]oxazepines via Two Tandem S N Ar Events. Part 1 – On the Importance of the Intermittent Smiles Rearrangement

AU - Sapegin, Alexander

AU - Krasavin, Mikhail

PY - 2019/4/4

Y1 - 2019/4/4

N2 - New bis-nucleophilic precursors to [1.4]oxazepines synthesized via S N Ar-Smiles rearrangement-S N Ar cascade have been designed. Employing them in base-promoted condensation with aromatic bis-electrophiles allowed differentiating between highly and poorly reactive substrates (i.e. those which can and cannot pass through the Smiles rearrangement barrier, respectively). The reactivity toward the desired course of cyclization can be restored by introducing electron-withdrawing substituents in the bis-electrophile precursor. This strongly argues for the importance of the Smiles rearrangement for the successful overall ring formation.

AB - New bis-nucleophilic precursors to [1.4]oxazepines synthesized via S N Ar-Smiles rearrangement-S N Ar cascade have been designed. Employing them in base-promoted condensation with aromatic bis-electrophiles allowed differentiating between highly and poorly reactive substrates (i.e. those which can and cannot pass through the Smiles rearrangement barrier, respectively). The reactivity toward the desired course of cyclization can be restored by introducing electron-withdrawing substituents in the bis-electrophile precursor. This strongly argues for the importance of the Smiles rearrangement for the successful overall ring formation.

KW - Nucleophilic aromatic substitution

KW - Oxazepines

KW - Privileged structures

KW - Smiles rearrangement

KW - Synthons

UR - http://www.scopus.com/inward/record.url?scp=85065096071&partnerID=8YFLogxK

UR - http://www.mendeley.com/research/convenient-assembly-privileged-heteroarenefused-benzo14oxazepines-via-two-tandem-s-n-ar-events-part

U2 - 10.1002/ejoc.201900263

DO - 10.1002/ejoc.201900263

M3 - Article

AN - SCOPUS:85065096071

JO - European Journal of Organic Chemistry

JF - European Journal of Organic Chemistry

SN - 1434-193X

ER -