{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,4]],"date-time":"2026-09-04T07:33:42Z","timestamp":1788507222710,"version":"build-2803163510"},"reference-count":43,"publisher":"Wiley","issue":"39","license":[{"start":{"date-parts":[[2012,8,13]],"date-time":"2012-08-13T00:00:00Z","timestamp":1344816000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2012,9,24]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The mechanism and sources of selectivity in the palladium\u2010catalyzed propargylic substitution reaction that involves phosphorus nucleophiles, and which yields predominantly allenylphosphonates and related compounds, have been studied computationally by means of density functional theory. Full free\u2010energy profiles are computed for both H\u2010phosphonate and H\u2010phosphonothioate substrates. The calculations show that the special behavior of H\u2010phosphonates among other heteroatom nucleophiles is indeed reflected in higher energy barriers for the attack on the central carbon atom of the allenyl\/propargyl ligand relative to the ligand\u2010exchange pathway, which leads to the experimentally observed products. It is argued that, to explain the preference of allenyl\u2010 versus propargyl\u2010phosphonate\/phosphonothioate formation in reactions that involve H\u2010phosphonates and H\u2010phosphonothioates, analysis of the complete free\u2010energy surfaces is necessary, because the product ratio is determined by different transition states in the respective branches of the catalytic cycle. In addition, these transition states change in going from a H\u2010phosphonate to a H\u2010phosphonothioate nucleophile.<\/jats:p>","DOI":"10.1002\/chem.201201026","type":"journal-article","created":{"date-parts":[[2012,8,13]],"date-time":"2012-08-13T08:25:52Z","timestamp":1344846352000},"page":"12424-12436","source":"Crossref","is-referenced-by-count":11,"title":["Computational Study of the Mechanism and Selectivity of Palladium\u2010Catalyzed Propargylic Substitution with Phosphorus Nucleophiles"],"prefix":"10.1002","volume":"18","author":[{"given":"J. Oscar C.","family":"Jim\u00e9nez\u2010Halla","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Marcin","family":"Kalek","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jacek","family":"Stawinski","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Fahmi","family":"Himo","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2012,8,13]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"Modern Allene Chemistry","year":"2004"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020024j"},{"key":"e_1_2_6_3_2","unstructured":"\u00a0"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20020816)114:16<3057::AID-ANGE3057>3.0.CO;2-S"},{"key":"e_1_2_6_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20020816)41:16<2933::AID-ANIE2933>3.0.CO;2-6"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200704729"},{"key":"e_1_2_6_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200704729"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200300628"},{"key":"e_1_2_6_6_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200300628"},{"key":"e_1_2_6_7_2","unstructured":"\u00a0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19951072305"},{"key":"e_1_2_6_8_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199525891"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200300352"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1039\/C0CC05640E"},{"key":"e_1_2_6_11_2","unstructured":"The notable exception was a reaction reported by Kozawa et\u2005al. in which heterocyclic amides that contain an allene moiety are obtained. Formation ofN\u2010allenes versus other products in this particular case can be attributed to the intramolecular nature of the reaction. See:"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(01)00870-X"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4039(02)00043-6"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo030123c"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol102121j"},{"key":"e_1_2_6_16_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201100119"},{"key":"e_1_2_6_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00090a060"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1039\/b315015a"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja043951b"},{"key":"e_1_2_6_20_2","unstructured":"Gaussian\u200503 Revision\u2005D.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. Pople Gaussian Inc. Wallingford CT 2004."},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.464913"},{"key":"e_1_2_6_22_2","unstructured":"\u00a0"},{"key":"e_1_2_6_23_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.448799"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1021\/ct8000409"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.20495"},{"key":"e_1_2_6_26_2","unstructured":"\u00a0"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9716997"},{"key":"e_1_2_6_28_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.10189"},{"key":"e_1_2_6_29_2","unstructured":"The initial application of a smaller model which contains a DPEPhos ligand core but with the phenyl groups on the phosphorus atoms replaced with hydrogen atoms led to a similar mechanism but the key energy values were incompatible with the experimental findings with regards to the selectivity. The results are therefore not discussed explicitly here."},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2006.02.049"},{"key":"e_1_2_6_30_3","doi-asserted-by":"publisher","DOI":"10.1021\/jo00876a042"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01304a032"},{"key":"e_1_2_6_32_2","unstructured":"This is the case under the experimental conditions since the reaction is carried out in a sealed tube which prevents CO2removal."},{"key":"e_1_2_6_33_2","unstructured":"There is an additional possibility of the ligand\u2010exchange process by means of a concerted proton transfer from the phosphorus to the oxygen of methoxide with a simultaneous replacement of the forming methanol with the oxygen of the phosphonate group at palladium. However despite multiple attempts we were unable to find the corresponding transition state and the structure always converged intoTS11\u201312. Therefore we concluded that the deprotonation must precede the ligand\u2010exchange process."},{"key":"e_1_2_6_34_2","unstructured":"\u00a0"},{"key":"e_1_2_6_35_2","doi-asserted-by":"publisher","DOI":"10.1039\/c39850001310"},{"key":"e_1_2_6_36_2","doi-asserted-by":"publisher","DOI":"10.1016\/0010-8545(94)80082-0"},{"key":"e_1_2_6_37_2","unstructured":"Because the main difference between the reactions involving1and1\u2010Sis the partial formation of a propargylic product in the latter case we have also evaluated whether the presence of sulfur has any influence on the barriers of the sigmatropic rearrangements that lead to17\u2009p\u2010S. However it was found thatTS13p\u201317p\u2010SandTS13a\u201317p\u2010Sare higher in energy than the corresponding reductive elimination transition stateTS14p\u201317p\u2010S and therefore they are not responsible for the observed deterioration of the selectivity. For details see the Supporting Information."},{"key":"e_1_2_6_38_2","first-page":"428","volume":"63","author":"Matveeva A. G.","year":"1993","journal-title":"Russ. J. Gen. Chem."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201201026","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201201026","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T12:48:59Z","timestamp":1760273339000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201201026"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2012,8,13]]},"references-count":43,"journal-issue":{"issue":"39","published-print":{"date-parts":[[2012,9,24]]}},"alternative-id":["10.1002\/chem.201201026"],"URL":"https:\/\/doi.org\/10.1002\/chem.201201026","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2012,8,13]]}}}