Synthesis of Pt compounds containing chiral (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives

Imre Tóth, Cornelis J. Elsevier, Johannes G. De Vries, J. Bakos, Wilberth J J Smeets, Anthony L. Spek

Research output: Contribution to journalArticle

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Abstract

Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)]n, 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)2, PtCl2(CH3CN)2 and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)]n, 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. but moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process. X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4.

Original languageEnglish
Pages (from-to)15-25
Number of pages11
JournalJournal of Organometallic Chemistry
Volume540
Issue number1-2
Publication statusPublished - Aug 1 1997

Fingerprint

Hydroformylation
phosphine
Styrene
crack opening displacement
Enantioselectivity
pentanes
styrenes
Conformations
monomers
Monomers
Ligands
Derivatives
Regioselectivity
ligands
Temperature
planar structures
room temperature
synthesis
Aldehydes
aldehydes

Keywords

  • Asymmetric hydroformylation
  • Dibenzophospholes
  • Ibuprofen
  • Platinum

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Synthesis of Pt compounds containing chiral (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives. / Tóth, Imre; Elsevier, Cornelis J.; De Vries, Johannes G.; Bakos, J.; Smeets, Wilberth J J; Spek, Anthony L.

In: Journal of Organometallic Chemistry, Vol. 540, No. 1-2, 01.08.1997, p. 15-25.

Research output: Contribution to journalArticle

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abstract = "Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)]n, 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)2, PtCl2(CH3CN)2 and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)]n, 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75{\%} e.e. but moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process. X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4.",
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T1 - Synthesis of Pt compounds containing chiral (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole) as ligand and their use in asymmetric hydroformylation of styrene derivatives

AU - Tóth, Imre

AU - Elsevier, Cornelis J.

AU - De Vries, Johannes G.

AU - Bakos, J.

AU - Smeets, Wilberth J J

AU - Spek, Anthony L.

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N2 - Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)]n, 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)2, PtCl2(CH3CN)2 and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)]n, 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. but moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process. X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4.

AB - Unlike bis(diphenyl)phosphine derivatives in general, (2S,4S)-pentane-2,4-diyl-bis(5H-dibenzo[b]phosphindole), S,S-BDBPP, gives a trans oligomeric compound [PtCl2(S,S-BDBPP)]n, 1, in reaction with dichloro-Pt precursors such as PtCl2(PhCN)2, PtCl2(CH3CN)2 and PtCl2(COD) at room temperature. Compound 1, which could be readily isolated, slowly rearranges in solutions at room temperature to the expected cis-monomer PtCl2(S,S-BDBPP), 3. Heating or the presence of PtCl2(COD) accelerates the transformation of compound 1 to 3. SnCl2 adducts of both compounds, trans-[PtCl(SnCl3)(S,S-BDBPP)]n, 2, and cis-PtCl(SnCl3)(S,S-BDBPP), 4, as well as the known cis-PtCl(SnCl3)(S,S-BDPP), 5, (S,S-BDPP = (2S,4S)-2,4-bis(diphenylphosphino)pentane) have been tested as catalysts in the asymmetric hydroformylation of p-isobutylstyrene. The phenyl analog 5 provides up to 75% e.e. but moderate yields to chiral 2-(4-isobutylphenyl)-2-propanal. Compared to this, the regioselectivity to the branched aldehyde is remarkably increased; however, the enantioselectivity is drastically decreased by the use of both dibenzophosphole derivatives 2 and 4. The similarities in the selectivities provided by 2 and 4 indicate that the trans oligomer 2 transforms to the cis-monomer 4 during the catalytic process. X-ray crystal structure determination of compound 3 shows a half-chair conformation for the chelate ring with a symmetric arrangement of dibenzophosphole groups. Besides a preference for the latter achiral conformation, the planar structure of the dibenzophosphole groups can also be considered as reason for the moderate enantioselectivities provided by 4.

KW - Asymmetric hydroformylation

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