Skip to main content
SpringerLink
Log in

Enantioselective Nickel Catalyzed Butadiene Hydroalkoxylation with Ethanol: from Experimental Results to Kinetics Parameters

  • Published:
Catalysis Letters Aims and scope Submit manuscript

Abstract

The enantioselective hydroalkoxylation of butadiene with ethanol has been performed in the presence of nickel-based catalysts and chiral diphosphine ligands. Ee’s up to 77% could be obtained from the use of atropoisomeric chiral ligands such as Segphos. The kinetics parameters of the reaction were determined using a qualitative kinetic model to better explain the l/b isomerization and racemization processes observed for long reaction times.

Graphic Abstract

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Scheme 2
Scheme 3
Fig. 1
Fig. 2
Fig. 3
Scheme 4
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  1. M. Beller, C. Bolm, Transition Metals for Organic Synthesis: Building Blocks and Fine Chemicals, Second Revised and Enlarged Edition (Wiley, 2004)

  2. Zeng X (2013) Recent advances in catalytic sequential reactions involving hydroelement addition to carbon–carbon multiple bonds. Chem Rev 113:68646–76900

    Google Scholar 

  3. Adamson NJ, Malcolmson SJ (2020) Catalytic enantio- and regioselective addition of nucleophiles in the intermolecular hydrofunctionalization of 1,3-dienes. ACS Catal 10:1060–1076

    CAS  Google Scholar 

  4. Long J, Wang P, Wang W, Li Y, Yin G (2019) Nickel/Brønsted acid-catalyzed chemo- and enantioselective intermolecular hydroamination of conjugated dienes. iScience 22:369–379

    CAS  PubMed  PubMed Central  Google Scholar 

  5. Bezzenine-Lafollee S, Gil R, Prim D, Hannedouche J. (2017). First-row late transition metals for catalytic alkene hydrofunctionalisation: recent advances in C-N, C-O and C-P bond formation. Molecules, 22: 1901/1–1901/29.

  6. Greenhalgh MD, Jones AS, Thomas SP (2015) Iron-Catalysed hydrofunctionalisation of alkenes and alkynes. ChemCatChem 7:190–222

    CAS  Google Scholar 

  7. Yadav JS, Antony A, Rao TS, Subba R, Basi V (2011) Recent progress in transition metal catalysed hydrofunctionalisation of less activated olefins. J Organomet Chem 696:16–36

    CAS  Google Scholar 

  8. Margrey KA, Nicewicz DA (2016) A general approach to catalytic alkene anti-Markovnikov hydrofunctionalization reactions via acridinium photoredox catalysis. Acc Chem Res 49:1997–2006

    CAS  PubMed  Google Scholar 

  9. Liu C, Bender CF, Han X, Widenhoefer RA (2007) Platinum-catalyzed hydrofunctionalization of unactivated alkenes with carbon, nitrogen and oxygen nucleophiles. Chem Commun 35:3607–3618

    Google Scholar 

  10. Obligacion JV, Chirik PJ (2018) Earth-abundant transition metal catalysts for alkene hydrosilylation and hydroboration. Nat Rev Chem 2:15–34

    CAS  PubMed  PubMed Central  Google Scholar 

  11. Chen J, Lu Z (2018) Asymmetric hydrofunctionalization of minimally functionalized alkenes via earth abundant transition metal catalysis. Org Chem Front 5:260–272

    CAS  Google Scholar 

  12. Ananikov VP, Tanaka MT. (2013). Topics in Organometallic Chemistry 43, Ed Springer.

  13. Hermann N, Vogelsang D, Behr A, Seidensticker T (2018) Homogeneously catalyzed 1,3-diene functionalization—A success story from laboratory to miniplant scale. ChemCatChem 10:5342–4365

    Google Scholar 

  14. Ibrahim AD, Entsminger SW, Zhu L, Fout AR (2016) A highly chemoselective cobalt catalyst for the hydrosilylation of alkenes using tertiary silanes and hydrosiloxanes. ACS Catal 6:3589–3593

    CAS  Google Scholar 

  15. Bini L, Müller C, Vogt D (2010) Ligand development in the Ni-catalyzed hydrocyanation of alkenes. Chem Commun 46:8325–8334

    CAS  Google Scholar 

  16. Mifleur A, Mortreux A, Suisse I, Sauthier M (2017) Synthesis of C4 chain glyceryl ethers via nickel-catalyzed butadiene hydroalkoxylation reaction. J Mol Catal A: Chem 427:25–30

    CAS  Google Scholar 

  17. Mifleur A, Ledru H, Lopes A, Suisse I, Mortreux A, Sauthier M (2016) Synthesis of short-chain alkenyl ethers from primary and bio-sourced alcohols via the nickel-catalyzed hydroalkoxylation reaction of butadiene and derivatives. Adv Synth Catal 358:110–121

    CAS  Google Scholar 

  18. Bigot S, Ibn El Alami MS, Mifleur A, Castanet Y, Suisse I, Mortreux A, Sauthier M (2013) Nickel-catalysed hydroalkoxylation reaction of 1,3-butadiene: ligand controlled selectivity for the efficient and atom-economical synthesis of alkylbutenyl ethers. Chem Eur J 19:9785–9788

    CAS  PubMed  Google Scholar 

  19. Nie SZ, Davison RT, Vy MD (2018) Enantioselective coupling of dienes and phosphine oxides. J Am Chem Soc 140:16450–16454

    CAS  PubMed  PubMed Central  Google Scholar 

  20. Mirzaei F, Han L, Tanaka M (2001) Palladium-catalyzed hydrophosphorylation of 1, 3-dienes leading to allylphosphonates. Tetrahedron Lett 42:297–299

    CAS  Google Scholar 

  21. Banerjee D, Junge K, Beller M (2014) Palladium-catalysed regioselective hydroamination of 1,3-dienes: synthesis of allylic amines. Org Chem Front 1:368–372

    CAS  Google Scholar 

  22. Goldfogel MJ, Roberts CC, Meek SJ (2014) Intermolecular hydroamination of 1,3-dienes catalyzed by bis(phosphine)carbodicarbene-rhodium complexes. J Am Chem Soc 136:6227–6230

    CAS  PubMed  Google Scholar 

  23. Yang XH, Lu A, Dong VM (2017) Intermolecular hydroamination of 1,3-dienes to generate homoallylic amine. J Am Chem Soc 139:14049–14052

    CAS  PubMed  PubMed Central  Google Scholar 

  24. Yang XH, Dong VM (2017) Rhodium-catalyzed hydrofunctionalization: enantioselective coupling of indolines and 1, 3-dienes. J Am Chem Soc 139:1774–1777

    CAS  PubMed  PubMed Central  Google Scholar 

  25. Banerjee D, Junge K, Beller M (2014) A general catalytic hydroamidation of 1,3-dienes: atom-efficient synthesis of N-allyl heterocycles, amides and sulphonamides. Angew Chem Int Ed 53:1630–1635

    CAS  Google Scholar 

  26. Satoh M, Nomoto Y, Miyaura N, Suzuki A (1989) New convenient approach to the preparation of (Z)-allylic boronates via catalytic 1, 4-hydroboration of 1, 3-dienes with catecholborane. Tetrahedron Lett 30:3789–3792

    CAS  Google Scholar 

  27. Trost BM (1995) Atom economy-a challenge for organic synthesis: homogeneous catalysis leads the way. Angew Chem Int Ed 34:259–281

    CAS  Google Scholar 

  28. Fassbach TA, Vorholt AJ, Leitner W (2019) The telomerization of 1, 3-dienes-A reaction grows up. ChemCatChem 11:1153–1166

    CAS  Google Scholar 

  29. Dewhirst KC (1967) Reaction of rhodium trichloride with dienes. J Org Chem 32:1297–1300

    CAS  Google Scholar 

  30. Kawazura H, Ohmori T (1972) On the catalytic addition of alcohols to 1, 3-butadiene with rhodium trichloride hydrates. Bull Chem Soc Jpn 45:2213–2214

    CAS  Google Scholar 

  31. Kawazura H, Takagaki T, Ishii Y (1975) The regioselective addition of alcohols to isoprene with rhodium trichloride hydrates. Bull Chem Soc Jpn 48:1949–1950

    CAS  Google Scholar 

  32. Fache E, Mercier C (1993) Addition of alcohols to isoprene catalyzed by hydrated rhodium trichloride: a way to improve the 1, 4-addition regioselectivity. J Mol Catal 78:21–30

    CAS  Google Scholar 

  33. Patrini R, Lami M, Marchionna M, Benvenuti F, Galleti AMR, Sbrana G (1998) Selective synthesis of octadienyl and butenyl ethers via reaction of 1, 3-butadiene with alcohols catalyzed by homogeneous palladium complexes. J Mol Catal 129(2–3):179–189

    CAS  Google Scholar 

  34. Utsunomiya M, Kawatsura M, Hartwig JF (2003) Palladium-catalyzed equilibrium addition of acidic OH groups across dienes. Angew Chem Int Ed 42:5865–5868

    CAS  Google Scholar 

  35. Shields TC, Walker WE (1971) Nickel-complex catalyzed telomerisation of butadiene with alcohols. J Chem Soc D 193–194.

  36. Weigert FJ, Drinkard WC (1973) The Ni(0)-catalyzed addition of phenol to butadiene. J Org Chem 38:335–337

    CAS  Google Scholar 

  37. Beger J, Duschek C, Füllbier H, Gaube W (1974) Diene oligomerization. IX. Nickel complex-catalyzed dimerization and telomerization of butadiene in hydroxy group-containing media. J Prakt Chem 316:26–42

    CAS  Google Scholar 

  38. Commereuc D, Chauvin Y (1974) Telomerization of butadiene with methanol using homogeneous catalysts of palladium and nickel. Bull Soc Chim Fr 3–4:652–656

    Google Scholar 

  39. Boelens H, Ter Heide R, Rijkens F (1968) Chemical structure and odor. VI Geraniol derivatives Am Perfum Cosmet 83:27–30

    CAS  Google Scholar 

  40. Behr A, Johnen L, Neubert P (2012) A sustainable route from the renewable myrcene to methyl ethers via direct hydroalkoxylation. Catal Sci Technol 2:88–92

    CAS  Google Scholar 

  41. Williams DBG, Sibiya MS, Van Heerden PS (2012) Efficient hydroalkoxylation of alkenes to generate octane-boosting ethers using recyclable metal triflates and highly active metal triflate/Brønsted acid-assisted catalysts. Fuel Process Technol 94:75–79

    CAS  Google Scholar 

  42. Chandrasekhar B, Ryu JS (2012) Gold-catalyzed intramolecular hydroalkoxylation/cyclization of conjugated dienyl alcohols. Tetrahedron 68:4805–4812

    CAS  Google Scholar 

  43. Mifleur A, Mérel D, Mortreux A, Suisse I, Capet F, Trivelli X, Sauthier M, MacGregor SA (2017) Deciphering the mechanism of the nickel-catalyzed hydroalkoxylation reaction: a combined experimental and computational Study. ACS Catal 7:6915–6923

    CAS  Google Scholar 

  44. Trost BM, Crawley ML (2003) Asymmetric transition-metal-catalyzed allylic alkylations: applications in total synthesis. Chem Rev 103:2921–2943

    CAS  PubMed  Google Scholar 

  45. Tran G, Mazet C (2019) Ni-catalyzed regioselective hydroalkoxylation of branched 1,3-dienes. Org Lett 21:9124–9127

    CAS  PubMed  Google Scholar 

  46. Kumobayashi H, Miura T, Sayo N, Saito T, Zhang X. (2001). Recent advances of BINAP chemistry in the industrial aspects. Synlett, 1055–1064.

  47. Trost BM, Van Vranken DL (1992) Asymmetric ligands for transition metal catalyzed reactions: 2-diphenylphosphinobenzoyl derivatives of C2 symmetrical diols and diamines. Angew Chem Int Ed 31:228–230

    Google Scholar 

Download references

Acknowledgements

We are grateful to the Region Nord-Pas de Calais for A.M.’s fellowship. We acknowledge the Ministry of Research and Technology, the Institut Universitaire de France, the ANR (project H2CAT: ANR-15-CE07-0018–01) and the CNRS for their financial support. We would like to express our gratitude to Dr Léo Violet and Dr Carole Mutschler for their precious advices.

Author information

Authors and Affiliations

  1. Univ. Lille, CNRS, Centrale Lille, Univ. Artois, UMR 8181 - UCCS - Unité de Catalyse Et Chimie du Solide, 59000, Lille, France

    Alexis Mifleur, Isabelle Suisse, André Mortreux & Mathieu Sauthier

Authors
  1. Alexis Mifleur
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Isabelle Suisse
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. André Mortreux
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Mathieu Sauthier
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Mathieu Sauthier.

Additional information

Dedicated to Prof. Alan Welch on the occasion of his retirement from Heriot-Watt University.

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Mifleur, A., Suisse, I., Mortreux, A. et al. Enantioselective Nickel Catalyzed Butadiene Hydroalkoxylation with Ethanol: from Experimental Results to Kinetics Parameters. Catal Lett 151, 27–35 (2021). https://doi.org/10.1007/s10562-020-03267-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10562-020-03267-z

Keyword

Search

Navigation