Abstract
A cascade reaction that generates pyrrolo- and pyridoindoline motifs from isocyanide precursors under phase-transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all-carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5-endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase-transfer catalysts have given promising selectivities to date.
| Language | English |
|---|---|
| Pages | 3005-3009 |
| Number of pages | 5 |
| Journal | Chemistry - A European Journal |
| Volume | 20 |
| Issue number | 11 |
| Early online date | 12 Feb 2014 |
| DOIs | |
| Publication status | Published - 10 Mar 2014 |
| Externally published | Yes |
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Keywords
- cascade reactions
- density functional calculations
- heterocycles
- hydrogen bonds
- isocyanides
- phase-transfer catalysis
Cite this
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Phase-transfer-catalysed synthesis of pyrroloindolines and pyridoindolines by a hydrogen-bond-assisted isocyanide cyclization cascade. / Knipe, Peter C.; Gredičak, Matija; Cernijenko, Artiom; Paton, Robert S.; Smith, Martin D.
In: Chemistry - A European Journal, Vol. 20, No. 11, 10.03.2014, p. 3005-3009.Research output: Contribution to journal › Article
TY - JOUR
T1 - Phase-transfer-catalysed synthesis of pyrroloindolines and pyridoindolines by a hydrogen-bond-assisted isocyanide cyclization cascade
AU - Knipe, Peter C.
AU - Gredičak, Matija
AU - Cernijenko, Artiom
AU - Paton, Robert S.
AU - Smith, Martin D.
PY - 2014/3/10
Y1 - 2014/3/10
N2 - A cascade reaction that generates pyrrolo- and pyridoindoline motifs from isocyanide precursors under phase-transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all-carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5-endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase-transfer catalysts have given promising selectivities to date.
AB - A cascade reaction that generates pyrrolo- and pyridoindoline motifs from isocyanide precursors under phase-transfer conditions is described. This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all-carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5-endo dig cyclization, rather than an anionic 6π electrocyclization. Investigations employing chiral phase-transfer catalysts have given promising selectivities to date.
KW - cascade reactions
KW - density functional calculations
KW - heterocycles
KW - hydrogen bonds
KW - isocyanides
KW - phase-transfer catalysis
UR - http://www.scopus.com/inward/record.url?scp=84897628699&partnerID=8YFLogxK
U2 - 10.1002/chem.201400192
DO - 10.1002/chem.201400192
M3 - Article
VL - 20
SP - 3005
EP - 3009
JO - Chemistry-a European Journal
T2 - Chemistry-a European Journal
JF - Chemistry-a European Journal
SN - 0947-6539
IS - 11
ER -