New Mechanistic Insights into the Copper-Free Heck–Cassar–Sonogashira Cross-Coupling Reaction
The copper-free Heck–Cassar–Sonogashira (HCS) reaction, known since 1975, nowadays represents one of the most powerful methods for C–C bond formation in organic synthesis with several industrial applications. Despite its great success, the mechanism is still under discussion, with several reported p...
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Published in | ACS catalysis Vol. 13; no. 18; pp. 12048 - 12061 |
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Main Authors | , , , , , , |
Format | Journal Article |
Language | English |
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American Chemical Society
15.09.2023
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Abstract | The copper-free Heck–Cassar–Sonogashira (HCS) reaction, known since 1975, nowadays represents one of the most powerful methods for C–C bond formation in organic synthesis with several industrial applications. Despite its great success, the mechanism is still under discussion, with several reported possible pathways. To clarify the copper-free HCS reaction mechanism, stoichiometric and catalytic reactions were carried out and monitored by 31P/1H NMR spectroscopy, HPLC, and GC chromatography. In particular, the investigation of the role of the base, mimicking the real catalytic conditions, highlighted the fact that secondary amines rapidly induce precatalyst reduction and decrease the energy barrier for the alkyne carbopalladation step. The results supported the mechanism via direct coordination of the terminal alkyne on the oxidative addition complex. Depending on the palladium counterion, and independent of the solvent, aromatic substitutions, temperature, and terminal alkyne substitution, these studies support two different pathways: with halides, a neutral route, and with the triflate, a cationic one. |
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AbstractList | The copper-free Heck–Cassar–Sonogashira (HCS) reaction, known since 1975, nowadays represents one of the most powerful methods for C–C bond formation in organic synthesis with several industrial applications. Despite its great success, the mechanism is still under discussion, with several reported possible pathways. To clarify the copper-free HCS reaction mechanism, stoichiometric and catalytic reactions were carried out and monitored by 31P/1H NMR spectroscopy, HPLC, and GC chromatography. In particular, the investigation of the role of the base, mimicking the real catalytic conditions, highlighted the fact that secondary amines rapidly induce precatalyst reduction and decrease the energy barrier for the alkyne carbopalladation step. The results supported the mechanism via direct coordination of the terminal alkyne on the oxidative addition complex. Depending on the palladium counterion, and independent of the solvent, aromatic substitutions, temperature, and terminal alkyne substitution, these studies support two different pathways: with halides, a neutral route, and with the triflate, a cationic one. |
Author | Ricci, Antonio Muzzi, Beatrice Fantoni, Tommaso Cabri, Walter Ferrazzano, Lucia Palladino, Chiara Tolomelli, Alessandra |
AuthorAffiliation | P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” Fresenius Kabi iPSUM Srl |
AuthorAffiliation_xml | – name: Fresenius Kabi iPSUM Srl – name: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” |
Author_xml | – sequence: 1 givenname: Chiara orcidid: 0000-0001-8245-9584 surname: Palladino fullname: Palladino, Chiara organization: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” – sequence: 2 givenname: Tommaso surname: Fantoni fullname: Fantoni, Tommaso organization: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” – sequence: 3 givenname: Lucia orcidid: 0000-0002-7083-2211 surname: Ferrazzano fullname: Ferrazzano, Lucia organization: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” – sequence: 4 givenname: Beatrice surname: Muzzi fullname: Muzzi, Beatrice – sequence: 5 givenname: Antonio surname: Ricci fullname: Ricci, Antonio organization: Fresenius Kabi iPSUM Srl – sequence: 6 givenname: Alessandra orcidid: 0000-0003-4202-1136 surname: Tolomelli fullname: Tolomelli, Alessandra organization: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” – sequence: 7 givenname: Walter orcidid: 0000-0001-7865-0474 surname: Cabri fullname: Cabri, Walter email: walter.cabri@unibo.it organization: P4Gi Lab − Projects for Green Innovation, Center of Chemical Catalysis, Department of Chemistry “Giacomo Ciamician” |
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CitedBy_id | crossref_primary_10_1021_acssuschemeng_3c04926 crossref_primary_10_1016_j_jorganchem_2024_123243 crossref_primary_10_1016_j_apcatb_2024_124310 crossref_primary_10_1039_D3CC03855F crossref_primary_10_1039_D3QO01919E |
Cites_doi | 10.1021/om800251s 10.1021/jo961464b 10.1021/acscatal.9b00007 10.1021/ja00022a026 10.3762/bjoc.10.36 10.1002/ejic.200400413 10.1021/jm100395q 10.1002/9783527819201 10.1021/jo202644g 10.1038/s42004-023-00849-x 10.1002/chem.202002013 10.1039/c2cs15288f 10.1021/jo00979a024 10.1021/ja00736a045 10.1039/C4DT01758G 10.1021/op0100100 10.1002/anie.200353015 10.1039/c39790000866 10.1021/om9709502 10.1016/S0022-328X(00)94048-8 10.1021/ol990872+ 10.1007/BF00912581 10.3390/catal8050202 10.1021/jo052423v 10.1039/c1cs15071e 10.1038/s41467-018-07081-5 10.1021/acs.orglett.0c01269 10.1016/j.checat.2022.12.002 10.1002/cssc.202100623 10.1021/ja9077528 10.1021/acs.inorgchem.2c00565 10.1021/cs200526x 10.1002/anie.201107017 10.1002/9783527677894.ch10 10.1016/S0040-4039(00)91094-3 10.3390/molecules27092668 10.1007/BF00947852 10.1021/om00004a038 10.1021/om060126q 10.1021/ol035632f 10.1039/c19680000006 10.1016/j.cattod.2021.09.022 10.1021/acs.oprd.6b00304 10.1016/S0022-328X(00)94049-X 10.1021/ar00049a001 10.1021/op050080x 10.1021/om00012a029 10.1021/acs.organomet.7b00010 |
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References | ref3/cit3 ref27/cit27 Huang W. S. (ref7/cit7a) 2010; 53 ref13/cit13a ref16/cit16 ref13/cit13b ref23/cit23 ref5/cit5b ref17/cit17 ref5/cit5c ref5/cit5a ref7/cit7l ref7/cit7g ref19/cit19 ref7/cit7f ref7/cit7e ref7/cit7d ref11/cit11b ref7/cit7i ref7/cit7h ref11/cit11a ref7/cit7c ref7/cit7b Colacot T. J. (ref2/cit2) 2020 ref24/cit24 ref18/cit18 ref15/cit15a ref9/cit9c ref9/cit9b ref9/cit9a ref15/cit15b ref25/cit25 ref15/cit15c ref8/cit8a ref10/cit10a ref8/cit8c ref10/cit10b ref8/cit8b ref21/cit21b ref21/cit21a ref9/cit9d ref26/cit26 ref6/cit6d ref14/cit14a ref12/cit12 ref14/cit14b ref20/cit20a ref22/cit22 ref20/cit20b ref4/cit4 ref6/cit6a ref1/cit1 ref6/cit6b ref6/cit6c |
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