Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation
A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd( ii ) ions, these hemilabile ligands showed the ability to form both P , S -chelates and complexes with two ligands P -monodentately b...
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| Veröffentlicht in: | Organic & biomolecular chemistry 2024-08, Vol.22 (31), p.6362-6369 |
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| creator | Gavrilov, Konstantin N Chuchelkin, Ilya V Gavrilov, Vladislav K Firsin, Ilya D Trunina, Valeria M Shiryaev, Alexey A Shkirdova, Alena O Bermesheva, Evgeniya V Tafeenko, Victor A Chernyshev, Vladimir V Zimarev, Vladislav S Goulioukina, Nataliya S |
| description | A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd(
ii
) ions, these hemilabile ligands showed the ability to form both
P
,
S
-chelates and complexes with two ligands
P
-monodentately bonded to the metal. The structures of the ligands and their complexes were determined by 2D NMR spectroscopy and X-ray diffraction. The use of these stereoselectors provided up to 95% ee in the classic Pd-catalyzed asymmetric allylic substitution reactions of (
E
)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 80% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, ee values of up to 90% with quantitative conversion were achieved in the Rh-catalyzed asymmetric hydrogenation of methyl esters of unsaturated acids. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed.
Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time. |
| doi_str_mv | 10.1039/d4ob00840e |
| format | Article |
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ii
) ions, these hemilabile ligands showed the ability to form both
P
,
S
-chelates and complexes with two ligands
P
-monodentately bonded to the metal. The structures of the ligands and their complexes were determined by 2D NMR spectroscopy and X-ray diffraction. The use of these stereoselectors provided up to 95% ee in the classic Pd-catalyzed asymmetric allylic substitution reactions of (
E
)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 80% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, ee values of up to 90% with quantitative conversion were achieved in the Rh-catalyzed asymmetric hydrogenation of methyl esters of unsaturated acids. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed.
Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.</description><identifier>ISSN: 1477-0520</identifier><identifier>ISSN: 1477-0539</identifier><identifier>EISSN: 1477-0539</identifier><identifier>DOI: 10.1039/d4ob00840e</identifier><identifier>PMID: 39045757</identifier><language>eng</language><publisher>England: Royal Society of Chemistry</publisher><subject>Acetic acid ; Alcohols ; Alkylation ; Asymmetry ; Catalytic converters ; Chelates ; Chemical reactions ; Esters ; Hydrogenation ; Ketoesters ; Ligands ; Magnetic resonance spectroscopy ; NMR spectroscopy ; Nucleophiles ; Palladium ; Rhodium ; Substitution reactions ; Sulfur ; Terpenes ; X-ray diffraction</subject><ispartof>Organic & biomolecular chemistry, 2024-08, Vol.22 (31), p.6362-6369</ispartof><rights>Copyright Royal Society of Chemistry 2024</rights><lds50>peer_reviewed</lds50><woscitedreferencessubscribed>false</woscitedreferencessubscribed><cites>FETCH-LOGICAL-c226t-b3f5f922b23b098eddbaa9060b0efc248e7228865a69d80ac7a4d688421b0dc83</cites><orcidid>0000-0002-3823-3999 ; 0000-0003-4749-7379 ; 0000-0002-6312-6087 ; 0000-0001-8514-7471 ; 0000-0002-3656-468X ; 0000-0003-3158-3790 ; 0000-0003-3002-2334</orcidid></display><links><openurl>$$Topenurl_article</openurl><openurlfulltext>$$Topenurlfull_article</openurlfulltext><thumbnail>$$Tsyndetics_thumb_exl</thumbnail><link.rule.ids>314,776,780,27903,27904</link.rule.ids><backlink>$$Uhttps://www.ncbi.nlm.nih.gov/pubmed/39045757$$D View this record in MEDLINE/PubMed$$Hfree_for_read</backlink></links><search><creatorcontrib>Gavrilov, Konstantin N</creatorcontrib><creatorcontrib>Chuchelkin, Ilya V</creatorcontrib><creatorcontrib>Gavrilov, Vladislav K</creatorcontrib><creatorcontrib>Firsin, Ilya D</creatorcontrib><creatorcontrib>Trunina, Valeria M</creatorcontrib><creatorcontrib>Shiryaev, Alexey A</creatorcontrib><creatorcontrib>Shkirdova, Alena O</creatorcontrib><creatorcontrib>Bermesheva, Evgeniya V</creatorcontrib><creatorcontrib>Tafeenko, Victor A</creatorcontrib><creatorcontrib>Chernyshev, Vladimir V</creatorcontrib><creatorcontrib>Zimarev, Vladislav S</creatorcontrib><creatorcontrib>Goulioukina, Nataliya S</creatorcontrib><title>Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation</title><title>Organic & biomolecular chemistry</title><addtitle>Org Biomol Chem</addtitle><description>A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd(
ii
) ions, these hemilabile ligands showed the ability to form both
P
,
S
-chelates and complexes with two ligands
P
-monodentately bonded to the metal. The structures of the ligands and their complexes were determined by 2D NMR spectroscopy and X-ray diffraction. The use of these stereoselectors provided up to 95% ee in the classic Pd-catalyzed asymmetric allylic substitution reactions of (
E
)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 80% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, ee values of up to 90% with quantitative conversion were achieved in the Rh-catalyzed asymmetric hydrogenation of methyl esters of unsaturated acids. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed.
Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.</description><subject>Acetic acid</subject><subject>Alcohols</subject><subject>Alkylation</subject><subject>Asymmetry</subject><subject>Catalytic converters</subject><subject>Chelates</subject><subject>Chemical reactions</subject><subject>Esters</subject><subject>Hydrogenation</subject><subject>Ketoesters</subject><subject>Ligands</subject><subject>Magnetic resonance spectroscopy</subject><subject>NMR spectroscopy</subject><subject>Nucleophiles</subject><subject>Palladium</subject><subject>Rhodium</subject><subject>Substitution reactions</subject><subject>Sulfur</subject><subject>Terpenes</subject><subject>X-ray diffraction</subject><issn>1477-0520</issn><issn>1477-0539</issn><issn>1477-0539</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2024</creationdate><recordtype>article</recordtype><recordid>eNpdkUtv1TAQhS0Eog_YsAdZYlMhhTqOE9vLtpSHVKkIwTryK72unDh4YonwL_jH-N5bLoiFNZbPN2dGPgi9qMnbmjTy3LKoCRGMuEfouGacV6Rt5OPDnZIjdAJwT0gteceeoqNGEtbylh-jXxfzHLxRi48TjgMe_Q9n8byJUE7KcA45DDnh4O_UZAFrBUUv7OLS7Kboy5uf8GdbFQ8V1p9FVbCOo1uSN1iFsBZ7DFnD4pe8G1OM8JfNPw2b1aZ456bdFs_Qk0EFcM8f6in69v7669XH6ub2w6eri5vKUNotlW6GdpCUatpoIoWzVislSUc0cYOhTDhOqRBdqzppBVGGK2Y7IRitNbFGNKfobO87p_g9O1j60YNxIajJxQx9s_1RKjivC_r6P_Q-5jSV7baU5JQL1hbqzZ4yKQIkN_Rz8qNKa1-TfhtU_47dXu6Cui7wqwfLrEdnD-ifZArwcg8kMAf1b9LNbwyGmyE</recordid><startdate>20240807</startdate><enddate>20240807</enddate><creator>Gavrilov, Konstantin N</creator><creator>Chuchelkin, Ilya V</creator><creator>Gavrilov, Vladislav K</creator><creator>Firsin, Ilya D</creator><creator>Trunina, Valeria M</creator><creator>Shiryaev, Alexey A</creator><creator>Shkirdova, Alena O</creator><creator>Bermesheva, Evgeniya V</creator><creator>Tafeenko, Victor A</creator><creator>Chernyshev, Vladimir V</creator><creator>Zimarev, Vladislav S</creator><creator>Goulioukina, Nataliya S</creator><general>Royal Society of Chemistry</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7QO</scope><scope>7T7</scope><scope>7TM</scope><scope>8FD</scope><scope>C1K</scope><scope>FR3</scope><scope>P64</scope><scope>7X8</scope><orcidid>https://orcid.org/0000-0002-3823-3999</orcidid><orcidid>https://orcid.org/0000-0003-4749-7379</orcidid><orcidid>https://orcid.org/0000-0002-6312-6087</orcidid><orcidid>https://orcid.org/0000-0001-8514-7471</orcidid><orcidid>https://orcid.org/0000-0002-3656-468X</orcidid><orcidid>https://orcid.org/0000-0003-3158-3790</orcidid><orcidid>https://orcid.org/0000-0003-3002-2334</orcidid></search><sort><creationdate>20240807</creationdate><title>Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation</title><author>Gavrilov, Konstantin N ; Chuchelkin, Ilya V ; Gavrilov, Vladislav K ; Firsin, Ilya D ; Trunina, Valeria M ; Shiryaev, Alexey A ; Shkirdova, Alena O ; Bermesheva, Evgeniya V ; Tafeenko, Victor A ; Chernyshev, Vladimir V ; Zimarev, Vladislav S ; Goulioukina, Nataliya S</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c226t-b3f5f922b23b098eddbaa9060b0efc248e7228865a69d80ac7a4d688421b0dc83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2024</creationdate><topic>Acetic acid</topic><topic>Alcohols</topic><topic>Alkylation</topic><topic>Asymmetry</topic><topic>Catalytic converters</topic><topic>Chelates</topic><topic>Chemical reactions</topic><topic>Esters</topic><topic>Hydrogenation</topic><topic>Ketoesters</topic><topic>Ligands</topic><topic>Magnetic resonance spectroscopy</topic><topic>NMR spectroscopy</topic><topic>Nucleophiles</topic><topic>Palladium</topic><topic>Rhodium</topic><topic>Substitution reactions</topic><topic>Sulfur</topic><topic>Terpenes</topic><topic>X-ray diffraction</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Gavrilov, Konstantin N</creatorcontrib><creatorcontrib>Chuchelkin, Ilya V</creatorcontrib><creatorcontrib>Gavrilov, Vladislav K</creatorcontrib><creatorcontrib>Firsin, Ilya D</creatorcontrib><creatorcontrib>Trunina, Valeria M</creatorcontrib><creatorcontrib>Shiryaev, Alexey A</creatorcontrib><creatorcontrib>Shkirdova, Alena O</creatorcontrib><creatorcontrib>Bermesheva, Evgeniya V</creatorcontrib><creatorcontrib>Tafeenko, Victor A</creatorcontrib><creatorcontrib>Chernyshev, Vladimir V</creatorcontrib><creatorcontrib>Zimarev, Vladislav S</creatorcontrib><creatorcontrib>Goulioukina, Nataliya S</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Biotechnology Research Abstracts</collection><collection>Industrial and Applied Microbiology Abstracts (Microbiology A)</collection><collection>Nucleic Acids Abstracts</collection><collection>Technology Research Database</collection><collection>Environmental Sciences and Pollution Management</collection><collection>Engineering Research Database</collection><collection>Biotechnology and BioEngineering Abstracts</collection><collection>MEDLINE - Academic</collection><jtitle>Organic & biomolecular chemistry</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Gavrilov, Konstantin N</au><au>Chuchelkin, Ilya V</au><au>Gavrilov, Vladislav K</au><au>Firsin, Ilya D</au><au>Trunina, Valeria M</au><au>Shiryaev, Alexey A</au><au>Shkirdova, Alena O</au><au>Bermesheva, Evgeniya V</au><au>Tafeenko, Victor A</au><au>Chernyshev, Vladimir V</au><au>Zimarev, Vladislav S</au><au>Goulioukina, Nataliya S</au><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation</atitle><jtitle>Organic & biomolecular chemistry</jtitle><addtitle>Org Biomol Chem</addtitle><date>2024-08-07</date><risdate>2024</risdate><volume>22</volume><issue>31</issue><spage>6362</spage><epage>6369</epage><pages>6362-6369</pages><issn>1477-0520</issn><issn>1477-0539</issn><eissn>1477-0539</eissn><abstract>A small library of easily prepared diamidophosphite-sulfides based on 1,3-thioether alcohols, primarily of terpenoid nature, was developed. Upon complexation with Pd(
ii
) ions, these hemilabile ligands showed the ability to form both
P
,
S
-chelates and complexes with two ligands
P
-monodentately bonded to the metal. The structures of the ligands and their complexes were determined by 2D NMR spectroscopy and X-ray diffraction. The use of these stereoselectors provided up to 95% ee in the classic Pd-catalyzed asymmetric allylic substitution reactions of (
E
)-1,3-diphenylallyl acetate with C- and N-nucleophiles and up to 80% ee in the Pd-mediated allylic alkylation of cinnamyl acetate with β-ketoesters. In addition, ee values of up to 90% with quantitative conversion were achieved in the Rh-catalyzed asymmetric hydrogenation of methyl esters of unsaturated acids. The effects of the structural parameters, reaction conditions and ligand-to-metal ratio on the catalytic results are discussed.
Diamidophosphite-thioethers with terpenoid bridging moieties have been prepared and used in asymmetric transition-metal catalysis for the first time.</abstract><cop>England</cop><pub>Royal Society of Chemistry</pub><pmid>39045757</pmid><doi>10.1039/d4ob00840e</doi><tpages>8</tpages><orcidid>https://orcid.org/0000-0002-3823-3999</orcidid><orcidid>https://orcid.org/0000-0003-4749-7379</orcidid><orcidid>https://orcid.org/0000-0002-6312-6087</orcidid><orcidid>https://orcid.org/0000-0001-8514-7471</orcidid><orcidid>https://orcid.org/0000-0002-3656-468X</orcidid><orcidid>https://orcid.org/0000-0003-3158-3790</orcidid><orcidid>https://orcid.org/0000-0003-3002-2334</orcidid></addata></record> |
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| ispartof | Organic & biomolecular chemistry, 2024-08, Vol.22 (31), p.6362-6369 |
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| language | eng |
| recordid | cdi_pubmed_primary_39045757 |
| source | Royal Society Of Chemistry Journals 2008-; Alma/SFX Local Collection |
| subjects | Acetic acid Alcohols Alkylation Asymmetry Catalytic converters Chelates Chemical reactions Esters Hydrogenation Ketoesters Ligands Magnetic resonance spectroscopy NMR spectroscopy Nucleophiles Palladium Rhodium Substitution reactions Sulfur Terpenes X-ray diffraction |
| title | Application of mixed phosphorus/sulfur ligands based on terpenoids in Pd-catalyzed asymmetric allylic substitution and Rh-catalyzed hydrogenation |
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