Rhodium-Catalyzed Pauson–Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C 1‑Diphosphine Ligand

Rhodium-Catalyzed Pauson–Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C 1‑Diphosphine Ligand

The asymmetric Pauson–Khand reaction catalyzed by [Rh­(COD)­(MaxPHOS)]­BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C 1-symmetry small-bit...

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Published in:Organometallics Vol. 34; no. 20; pp. 4989 - 4993
Main Authors: Cristóbal-Lecina, Edgar, Costantino, Andrea R, Grabulosa, Arnald, Riera, Antoni, Verdaguer, Xavier
Format: Journal Article
Language:English
Published: American Chemical Society 26-10-2015
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Abstract The asymmetric Pauson–Khand reaction catalyzed by [Rh­(COD)­(MaxPHOS)]­BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C 1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.
AbstractList The asymmetric Pauson–Khand reaction catalyzed by [Rh­(COD)­(MaxPHOS)]­BF4 is described. Several 1,6-enynes have been chosen as model substrates affording moderate yields and selectivities of up to 86% ee. Besides binap-type ligands, we have demonstrated that the P-stereogenic C 1-symmetry small-bite-angle ligand MaxPHOS is a viable ligand in this process. The formation of [2+2+2] cycloaddition compounds has shown to be a competitive process. A mechanism is proposed to account for the observed results. The intermediate rhodium dicarbonyl complex 6 was synthesized, and its solid-state structure was elucidated by X-ray crystallography.
Author Riera, Antoni
Verdaguer, Xavier
Cristóbal-Lecina, Edgar
Costantino, Andrea R
Grabulosa, Arnald
AuthorAffiliation CONICET, Argentina, Instituto de Química del Sur (INQUISUR), Departamento de Química
Departament de Química Inorgànica
Universidad Nacional del Sur
Universitat de Barcelona
Departament de Química Orgànica
AuthorAffiliation_xml – name: Universidad Nacional del Sur
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  givenname: Edgar
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  fullname: Cristóbal-Lecina, Edgar
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  surname: Costantino
  fullname: Costantino, Andrea R
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  surname: Grabulosa
  fullname: Grabulosa, Arnald
– sequence: 4
  givenname: Antoni
  surname: Riera
  fullname: Riera, Antoni
  email: xavier.verdaguer@irbbarcelona.org
– sequence: 5
  givenname: Xavier
  surname: Verdaguer
  fullname: Verdaguer, Xavier
  email: antoni.riera@irbbarcelona.org
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Title Rhodium-Catalyzed Pauson–Khand Reaction Using a Small-Bite-Angle P‑Stereogenic C 1‑Diphosphine Ligand
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