{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T03:32:42Z","timestamp":1760239962443,"version":"build-2065373602"},"reference-count":43,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2019,2,5]],"date-time":"2019-02-05T00:00:00Z","timestamp":1549324800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Molecules"],"abstract":"<jats:p>A simple, highly efficient synthesis of a series of novel chiral non-racemic rigid tetracyclic phosphorus ligands, applicable in important chemical asymmetric transformations, was performed. In a tandem cross-coupling\/C-H bond activation reaction, a well-recognised and readily available ligand (R,R)-NORPHOS was used as the starting material. The palladium complexes of new ligands were obtained and characterised on the example of a crystalline dichloropalladium complex of [(1R,2R,9S,10S,11R,12R)-4-phenyltetracyclo[8.2.1.02,9.03,8]trideca-3,5,7-triene-11,12-diyl]bis(diphenylphosphane). A notably high activity and stereoselectivity of the palladium catalysts based on the new ligands were confirmed in a model asymmetric allylic substitution reaction. Herein, we discuss the geometry of the palladium complexes formed and its impact on the efficiency of the catalysts. A comparison of their geometric features with other bis(phosphane) ligand complexes found in the Cambridge Structural Database and built density functional theory (DFT) commutated models is also presented and rationalised.<\/jats:p>","DOI":"10.3390\/molecules24030571","type":"journal-article","created":{"date-parts":[[2019,2,6]],"date-time":"2019-02-06T03:03:05Z","timestamp":1549422185000},"page":"571","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":10,"title":["New Rigid Polycyclic Bis(phosphane) for Asymmetric Catalysis"],"prefix":"10.3390","volume":"24","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-0969-4689","authenticated-orcid":false,"given":"K. Micha\u0142","family":"Pietrusiewicz","sequence":"first","affiliation":[{"name":"Faculty of Chemistry, Maria Curie-Sklodowska University, 33-Gliniana St., 20-031 Lublin, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Katarzyna","family":"Szwaczko","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Maria Curie-Sklodowska University, 33-Gliniana St., 20-031 Lublin, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5765-4641","authenticated-orcid":false,"given":"Barbara","family":"Miros\u0142aw","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Maria Curie-Sklodowska University, 33-Gliniana St., 20-031 Lublin, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Izabela","family":"Dyba\u0142a","sequence":"additional","affiliation":[{"name":"Faculty of Pharmacy, Medical University of Lublin, 4<sup>A<\/sup>-Chod\u017aki St., 20-093 Lublin, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Radomir","family":"Jasi\u0144ski","sequence":"additional","affiliation":[{"name":"Department of Organic Chemistry, Cracow University of Technology, 24-Warszawska St., 31-155 Cracow, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5571-1593","authenticated-orcid":false,"given":"Oleg M.","family":"Demchuk","sequence":"additional","affiliation":[{"name":"Faculty of Chemistry, Maria Curie-Sklodowska University, 33-Gliniana St., 20-031 Lublin, Poland"},{"name":"Pharmaceutical Research Institute, 8-Rydygiera St., 01-793 Warsaw, Poland"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"1968","published-online":{"date-parts":[[2019,2,5]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","unstructured":"Oestreich, M. (2009). The Mizoroki-Heck Reaction, Wiley.","DOI":"10.1002\/9780470716076"},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"3009","DOI":"10.1021\/cr9903048","article-title":"The Heck Reaction as a Sharpening Stone of Palladium Catalysis","volume":"100","author":"Beletskaya","year":"2000","journal-title":"Chem. Rev."},{"key":"ref_3","doi-asserted-by":"crossref","unstructured":"de Meijere, A., Br\u00e4se, S., and Oestreich, M. (2014). Metal-Catalyzed Cross-Coupling Reactions and More, Wiley. 3 Volume Set.","DOI":"10.1002\/9783527655588"},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"c13","DOI":"10.1016\/0022-328X(85)87247-8","article-title":"Palladium-catalyzed synthesis of 1,2,3,4,4a,12b-hexahydro-1,4-methanotriphenylenes","volume":"286","author":"Catellani","year":"1985","journal-title":"J. Organomet. Chem."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"863","DOI":"10.1038\/nchem.2372","article-title":"Palladium-catalysed norbornene-mediated C\u2212H functionalization of arenes","volume":"7","author":"Ye","year":"2015","journal-title":"Nat. Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"1697","DOI":"10.1002\/anie.201712393","article-title":"Direct Annulation between Aryl Iodides and Epoxides through Palladium\/Norbornene Cooperative Catalysis","volume":"57","author":"Li","year":"2017","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"4346","DOI":"10.1002\/cctc.201800940","article-title":"Enhancing Reactivity and Selectivity of Aryl Bromides: A Complementary Approach to Dibenzo[b,f]azepine Derivatives","volume":"10","author":"Casnati","year":"2018","journal-title":"ChemCatChem Catal."},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"3407","DOI":"10.1039\/C8CC01062E","article-title":"Synthesis of indolines via a palladium\/norbornene-catalyzed reaction of aziridines with aryl iodides","volume":"54","author":"Liu","year":"2018","journal-title":"Chem. Commun."},{"key":"ref_9","doi-asserted-by":"crossref","unstructured":"Tundo, P., He, L.-N., Lokteva, E., and Mota, C. (2016). The Halogen-Less Catalytic Transition Metal-Mediated Cross-Coupling Reactions: A Sustainable Alternative for Utilisation of Organohalides. Chemistry Beyond Chlorine, Springer.","DOI":"10.1007\/978-3-319-30073-3"},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"620","DOI":"10.1002\/anie.197906201","article-title":"Asymmetric Hydrogenation of (Z)-(Acetylamino)-cinnamic Acid by a Rh\/norphos Catalyst","volume":"18","author":"Brunner","year":"1979","journal-title":"Angew. Chem. Int. Ed. Engl."},{"key":"ref_11","unstructured":"Marchand, A.P., Romanski, J., and Kumar, T.P. (2003). (R,R)-(-)-NORPHOS and (S,S)-(+)-NORPHOS. e-EROS: Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, Ltd."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"3491","DOI":"10.1016\/j.tetlet.2016.06.104","article-title":"Straightforward approach to norbornene core based chiral ligands by tandem cross dehydrogenative coupling reactions","volume":"57","author":"Szwaczko","year":"2016","journal-title":"Tetrahedron Lett."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"6668","DOI":"10.1016\/j.tet.2016.08.087","article-title":"Readily available catalysts for demanding Suzuki\u2013Miyaura couplings under mild conditions","volume":"72","author":"Demchuk","year":"2016","journal-title":"Tetrahedron"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"7717","DOI":"10.1039\/C8OB02265H","article-title":"Synthesis of highly rigid phosphine\u2013oxazoline ligands for palladium-catalyzed asymmetric allylic alkylation","volume":"16","author":"Qiu","year":"2018","journal-title":"Org. Biomol. Chem."},{"key":"ref_15","doi-asserted-by":"crossref","unstructured":"Snieckus, V., Demchuk, O., Yoruk, B., and Blackburn, T. (2006). A Mixed Naphthyl-Phenyl Phosphine Ligand Motif for Suzuki, Heck, and Hydrodehalogenation Reactions. Synlett, 2908\u20132913.","DOI":"10.1055\/s-2006-951538"},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"633","DOI":"10.1351\/PAC-CON-10-08-06","article-title":"Rational design of novel ligands for environmentally benign cross-coupling reactions","volume":"83","author":"Demchuk","year":"2011","journal-title":"Pure Appl. Chem."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"6409","DOI":"10.1021\/ja00333a052","article-title":"Displacive transfer of a phenyl group from triphenylphosphine to a metal atom: Synthesis and molecular structure of the dibenzamidediphenyldiruthenium compound Ru2Ph2(PhCONH)2[Ph2POC(Ph)N]2","volume":"106","author":"Chakravarty","year":"1984","journal-title":"J. Am. Chem. Soc."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"5752","DOI":"10.1039\/C8CC02571A","article-title":"Pd-Catalyzed reductive heck reaction of olefins with aryl bromides for Csp2\u2013Csp3 bond formation","volume":"54","author":"Jin","year":"2018","journal-title":"Chem. Commun."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"9332","DOI":"10.1021\/jacs.8b03619","article-title":"Palladium-Catalyzed Regiocontrollable Reductive Heck Reaction of Unactivated Aliphatic Alkenes","volume":"140","author":"Wang","year":"2018","journal-title":"J. Am. Chem. Soc."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"5502","DOI":"10.1021\/j100377a017","article-title":"Calculation of puckered rings with analytical gradients","volume":"94","author":"Cremer","year":"1990","journal-title":"J. Phys. Chem."},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"171","DOI":"10.1107\/S2052520616003954","article-title":"The Cambridge Structural Database","volume":"72","author":"Groom","year":"2016","journal-title":"Acta Crystallogr. Sect. B Struct. Sci. Cryst. Eng. Mater."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"3815","DOI":"10.1039\/C0DT00253D","article-title":"Surprising photochemical reactivity and visible light-driven energy transfer in heterodimetallic complexes","volume":"40","author":"Eller","year":"2011","journal-title":"Dalton Trans."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"109","DOI":"10.1021\/ic00079a021","article-title":"Thermal dimerization of 1-substituted-3,4-dimethylphospholes within the coordination sphere of platinum(II)","volume":"33","author":"Wilson","year":"1994","journal-title":"Inorg. Chem."},{"key":"ref_24","doi-asserted-by":"crossref","first-page":"4832","DOI":"10.1021\/om3003812","article-title":"Regioselective Hydromethoxycarbonylation of Terminal Alkynes Catalyzed by Palladium(II)\u2013Tetraphos Complexes","volume":"31","author":"Oberhauser","year":"2012","journal-title":"Organometallics"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"913","DOI":"10.1016\/S0277-5387(00)00332-6","article-title":"Palladium(II), platinum(II), and platinum(IV) complexes containing trans-1,2-bis(diphenylphosphino)ethene or cis,trans,cis-1,2,3,4-tetrakis(diphenylphosphino)cyclobutane: Complete X-ray structural characterization of binuclear compounds","volume":"19","author":"Oberhauser","year":"2000","journal-title":"Polyhedron"},{"key":"ref_26","doi-asserted-by":"crossref","first-page":"5121","DOI":"10.1002\/ejic.201300636","article-title":"Versatile Supramolecular Coordination Behaviour of a Bis(bidentate) Tetraphosphane","volume":"2013","author":"Strabler","year":"2013","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"215","DOI":"10.1007\/s00214-007-0310-x","article-title":"The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: Two new functionals and systematic testing of four M06-class functionals and 12 other functionals","volume":"120","author":"Zhao","year":"2007","journal-title":"Theor. Chem. Acc."},{"key":"ref_28","unstructured":"Frisch, M.J., Trucks, G.W., Schlegel, H.B., Scuseria, G.E., Robb, M.A., Cheeseman, J.R., Scalmani, G., Barone, V., Mennucci, B., and Petersson, G.A. (2010). Gaussian 09, Revision B.01, Gaussian Inc."},{"key":"ref_29","first-page":"1","article-title":"A Quantum-Chemical DFT Approach to Elucidation of the Chirality Transfer Mechanism of the Enantioselective Suzuki\u2013Miyaura Cross-Coupling Reaction","volume":"2017","author":"Demchuk","year":"2017","journal-title":"J. Chem."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"1877","DOI":"10.1007\/s00706-018-2227-6","article-title":"Regiospecific formation of the nitromethyl-substituted 3-phenyl-4,5-dihydroisoxazole via [3\u2009+\u20092] cycloaddition","volume":"149","author":"Babyuk","year":"2018","journal-title":"Monatshefte f\u00fcr Chemie (Chem. Mon.)"},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"441","DOI":"10.1002\/hc.21279","article-title":"New Insights into the Mechanism of Reduction of Tertiary Phosphine Oxides by Means of Phenylsilane","volume":"26","author":"Demchuk","year":"2015","journal-title":"Heteroat. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"29","DOI":"10.1016\/j.jfluchem.2014.01.007","article-title":"Molecular mechanism of thermal decomposition of fluoronitroazoxy compounds: DFT computational study","volume":"160","year":"2014","journal-title":"J. Fluor. Chem."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"66","DOI":"10.1002\/poc.3237","article-title":"2-Methoxynaphthylnaphthoquinone and its solvate: Synthesis and structure-properties relationship","volume":"27","author":"Demchuk","year":"2014","journal-title":"J. Phys. Org. Chem."},{"key":"ref_34","doi-asserted-by":"crossref","first-page":"1006","DOI":"10.1002\/poc.2998","article-title":"Relationship between structure and efficiency of atropisomeric phosphine ligands in homogeneous catalytic asymmetric hydrogenation","volume":"25","author":"Demchuk","year":"2012","journal-title":"J. Phys. Org. Chem."},{"key":"ref_35","doi-asserted-by":"crossref","first-page":"245","DOI":"10.1080\/10426507.2015.1064921","article-title":"Organophosphorus ligands: Recent developments in design, synthesis, and application in environmentally benign catalysis","volume":"191","author":"Demchuk","year":"2015","journal-title":"Phosphorus Sulfur Silicon Relat. Elem."},{"key":"ref_36","doi-asserted-by":"crossref","first-page":"436","DOI":"10.1016\/j.molstruc.2018.10.033","article-title":"Synthesis, crystal structure, DFT calculations and molecular docking of l-pyroglutamic acid","volume":"1178","author":"Issa","year":"2019","journal-title":"J. Mol. Struct."},{"key":"ref_37","doi-asserted-by":"crossref","unstructured":"Jin, M.-J., Takale, V.B., Sarkar, M.S., and Kim, Y.-M. (2006). Highly enantioselective Pd-catalyzed allylic alkylation using new chiral ferrocenylphosphinoimidazolidine ligands. Chem. Commun., 663.","DOI":"10.1039\/b515283f"},{"key":"ref_38","doi-asserted-by":"crossref","first-page":"663","DOI":"10.1016\/S0957-4166(00)86120-0","article-title":"Palladium-catalyzed asymmetric allylic alkylation using dimethyl malonate and its derivatives as nucleophile","volume":"2","author":"Yamaguchi","year":"1991","journal-title":"Tetrahedron Asymmetry"},{"key":"ref_39","doi-asserted-by":"crossref","first-page":"961","DOI":"10.1134\/S1063774514070128","article-title":"The crystal structure of (1RS,4RS,5RS,6SR)-5-cyano-5-nitro-6-phenyl-bicyclo[2.2.1]hept-2-ene","volume":"59","author":"Ponikiewski","year":"2014","journal-title":"Crystallogr. Rep."},{"key":"ref_40","doi-asserted-by":"crossref","first-page":"327","DOI":"10.1007\/s00706-012-0885-3","article-title":"Experimental and theoretical studies of Diels\u2013Alder reaction between methyl (Z)-2-nitro-3-(4-nitrophenyl)-2-propenoate and cyclopentadiene","volume":"144","author":"Kwiatkowska","year":"2013","journal-title":"Monatshefte f\u00fcr Chemie (Chem. Mon.)"},{"key":"ref_41","unstructured":"Rigaku Oxford Diffraction (2015). CrysAlis PRO ver. 1.171.38.46, Rigaku Oxford Diffraction."},{"key":"ref_42","doi-asserted-by":"crossref","first-page":"3","DOI":"10.1107\/S2053273314026370","article-title":"SHELXT\u2014Integrated space-group and crystal-structure determination","volume":"71","author":"Sheldrick","year":"2015","journal-title":"Acta Crystallogr. Sect. A Found. Adv."},{"key":"ref_43","doi-asserted-by":"crossref","first-page":"339","DOI":"10.1107\/S0021889808042726","article-title":"OLEX2: A complete structure solution, refinement and analysis program","volume":"42","author":"Dolomanov","year":"2009","journal-title":"J. Appl. Crystallogr."}],"container-title":["Molecules"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/3\/571\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T12:31:04Z","timestamp":1760185864000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/1420-3049\/24\/3\/571"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2019,2,5]]},"references-count":43,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2019,2]]}},"alternative-id":["molecules24030571"],"URL":"https:\/\/doi.org\/10.3390\/molecules24030571","relation":{},"ISSN":["1420-3049"],"issn-type":[{"type":"electronic","value":"1420-3049"}],"subject":[],"published":{"date-parts":[[2019,2,5]]}}}