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Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds
The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)‐Skewphos (2) and (S,S)‐Skewphos (3)) are easily obtained in 85–88 % yield through a one‐pot synthesis from [RuCl(2)(PPh(3))(3)], the diphosphine and 2,2′:6′,2′′‐terpyridine (tpy) in 1‐bu...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828271/ https://www.ncbi.nlm.nih.gov/pubmed/36001351 http://dx.doi.org/10.1002/chem.202201722 |
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author | Ballico, Maurizio Alessi, Dario Jandl, Christian Lovison, Denise Baratta, Walter |
author_facet | Ballico, Maurizio Alessi, Dario Jandl, Christian Lovison, Denise Baratta, Walter |
author_sort | Ballico, Maurizio |
collection | PubMed |
description | The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)‐Skewphos (2) and (S,S)‐Skewphos (3)) are easily obtained in 85–88 % yield through a one‐pot synthesis from [RuCl(2)(PPh(3))(3)], the diphosphine and 2,2′:6′,2′′‐terpyridine (tpy) in 1‐butanol. Treatment of 1–3 with NaPF(6) in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF(6) (PP=dppp (1 a), (R,R)‐Skewphos (2 a) and (S,S)‐Skewphos (3 a)). Reaction of [RuCl(2)(PPh(3))(3)] with (S,R)‐Josiphos or (R)‐BINAP in toluene, followed by treatment with tpy in 1‐butanol and finally with NaPF(6) in MeOH gives [RuCl(PP)(tpy)]PF(6) (PP=(S,R)‐Josiphos (4 a), (R)‐BINAP (5 a)) isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a, 4 a have been characterized by single crystal X‐ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2‐propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h(−1). The chiral enantiomers 2, 2 a and 3, 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)‐ and (R)‐1‐phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2‐propanol mixture. |
format | Online Article Text |
id | pubmed-9828271 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-98282712023-01-10 Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds Ballico, Maurizio Alessi, Dario Jandl, Christian Lovison, Denise Baratta, Walter Chemistry Research Articles The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP=dppp (1), (R,R)‐Skewphos (2) and (S,S)‐Skewphos (3)) are easily obtained in 85–88 % yield through a one‐pot synthesis from [RuCl(2)(PPh(3))(3)], the diphosphine and 2,2′:6′,2′′‐terpyridine (tpy) in 1‐butanol. Treatment of 1–3 with NaPF(6) in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF(6) (PP=dppp (1 a), (R,R)‐Skewphos (2 a) and (S,S)‐Skewphos (3 a)). Reaction of [RuCl(2)(PPh(3))(3)] with (S,R)‐Josiphos or (R)‐BINAP in toluene, followed by treatment with tpy in 1‐butanol and finally with NaPF(6) in MeOH gives [RuCl(PP)(tpy)]PF(6) (PP=(S,R)‐Josiphos (4 a), (R)‐BINAP (5 a)) isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a, 4 a have been characterized by single crystal X‐ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2‐propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h(−1). The chiral enantiomers 2, 2 a and 3, 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)‐ and (R)‐1‐phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2‐propanol mixture. John Wiley and Sons Inc. 2022-09-27 2022-11-21 /pmc/articles/PMC9828271/ /pubmed/36001351 http://dx.doi.org/10.1002/chem.202201722 Text en © 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH https://creativecommons.org/licenses/by/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Research Articles Ballico, Maurizio Alessi, Dario Jandl, Christian Lovison, Denise Baratta, Walter Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title | Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title_full | Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title_fullStr | Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title_full_unstemmed | Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title_short | Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds |
title_sort | terpyridine diphosphine ruthenium complexes as efficient photocatalysts for the transfer hydrogenation of carbonyl compounds |
topic | Research Articles |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9828271/ https://www.ncbi.nlm.nih.gov/pubmed/36001351 http://dx.doi.org/10.1002/chem.202201722 |
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