{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,24]],"date-time":"2026-08-24T09:35:47Z","timestamp":1787564147239,"version":"build-2736575974"},"reference-count":47,"publisher":"American Chemical Society (ACS)","issue":"44","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Am. Chem. Soc."],"published-print":{"date-parts":[[2008,11,5]]},"DOI":"10.1021\/ja806278e","type":"journal-article","created":{"date-parts":[[2008,10,8]],"date-time":"2008-10-08T07:01:28Z","timestamp":1223449288000},"page":"14471-14473","source":"Crossref","is-referenced-by-count":104,"title":["Counterintuitive Kinetics in Tsuji-Trost Allylation: Ion-Pair Partitioning and Implications for Asymmetric Catalysis"],"prefix":"10.1021","volume":"130","author":[{"given":"Louise A.","family":"Evans","sequence":"first","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalie","family":"Fey","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jeremy N.","family":"Harvey","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"David","family":"Hose","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guy C.","family":"Lloyd-Jones","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul","family":"Murray","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"A. Guy","family":"Orpen","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert","family":"Osborne","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gareth J. J.","family":"Owen-Smith","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mark","family":"Purdie","sequence":"additional","affiliation":[{"name":"University of Bristol, Cantock\u2019s Close, Bristol, BS8 1TS, U.K., AstraZeneca, Avlon Works, Severn Road, Hallen, Bristol BS10 7ZE, and AstraZeneca, Bakewell Road, Loughborough, LE11 5RH, U.K."}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2008,10,8]]},"reference":[{"key":"ref1\/cit1a","doi-asserted-by":"crossref","first-page":"4387","DOI":"10.1016\/S0040-4039(00)71674-1","volume":"6","author":"Tsuji J.","year":"1965","journal-title":"Tetrahedron Lett."},{"key":"ref1\/cit1b","doi-asserted-by":"crossref","first-page":"292","DOI":"10.1021\/ja00782a080","volume":"95","author":"Trost B. M.","year":"1973","journal-title":"J. Am. Chem. Soc."},{"key":"ref2\/cit2a","doi-asserted-by":"crossref","first-page":"3821","DOI":"10.1016\/S0040-4039(01)98599-5","volume":"11","author":"Atkins K. E.","year":"1970","journal-title":"Tetrahedron Lett."},{"key":"ref2\/cit2b","unstructured":"bSee reference 1 cited in ref3afor an extensive list of reviews."},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"258","DOI":"10.1002\/anie.200605113","volume":"47","author":"Lu Z.","year":"2007","journal-title":"Angew Chem., Int. Ed."},{"key":"ref3\/cit3b","volume-title":"Catalytic Asymmetric Synthesis,","author":"Trost B. M.","year":"2000","edition":"2"},{"key":"ref3\/cit3c","volume-title":"Comprehensive Asymmetric Catalysis","author":"Pfaltz A.","year":"1999"},{"key":"ref4\/cit4a","doi-asserted-by":"crossref","first-page":"2046","DOI":"10.1021\/ja00293a039","volume":"107","author":"Mackenzie P. B.","year":"1985","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4b","doi-asserted-by":"crossref","first-page":"133","DOI":"10.1016\/0022-328X(87)85181-1","volume":"335","author":"\u00c5kermark B.","year":"1987","journal-title":"J. Organomet. Chem."},{"key":"ref4\/cit4c","doi-asserted-by":"crossref","first-page":"3118","DOI":"10.1002\/(SICI)1521-3773(19981204)37:22<3118::AID-ANIE3118>3.0.CO;2-G","volume":"37","author":"Ramdeehul S.","year":"1998","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref4\/cit4d","doi-asserted-by":"crossref","first-page":"4202","DOI":"10.1002\/chem.200204657","volume":"9","author":"Gais H.-J.","year":"2003","journal-title":"Chem.\u2014Eur. J."},{"key":"ref4\/cit4da","unstructured":"Studies reporting on the kinetics of\n                      stoichiometric amination\n                      of \u03c0-allyl Pd complexes:"},{"key":"ref4\/cit4e","doi-asserted-by":"crossref","first-page":"C22","DOI":"10.1016\/0022-328X(88)87036-0","volume":"349","author":"Vitagliano A.","year":"1988","journal-title":"J. Organomet. Chem."},{"key":"ref4\/cit4f","doi-asserted-by":"crossref","first-page":"343","DOI":"10.1002\/(SICI)1521-3773(19990201)38:3<343::AID-ANIE343>3.0.CO;2-X","volume":"38","author":"Kuhne O.","year":"1999","journal-title":"Angew Chem. Int. Ed."},{"key":"ref4\/cit4g","doi-asserted-by":"crossref","first-page":"1875","DOI":"10.1021\/om060686p","volume":"26","author":"Amatore C.","year":"2007","journal-title":"Organometallics"},{"key":"ref4\/cit4h","doi-asserted-by":"crossref","first-page":"466","DOI":"10.1002\/(SICI)1521-3765(19990201)5:2<466::AID-CHEM466>3.0.CO;2-E","volume":"5","author":"Amatore C.","year":"1999","journal-title":"Chem.\u2014Eur. J."},{"key":"ref4\/cit4i","doi-asserted-by":"crossref","first-page":"1273","DOI":"10.1002\/1521-3765(20010316)7:6<1273::AID-CHEM1273>3.0.CO;2-7","volume":"7","author":"Amatore C.","year":"2001","journal-title":"Chem.\u2014Eur. J."},{"key":"ref4\/cit4j","doi-asserted-by":"crossref","first-page":"3237","DOI":"10.1016\/S0013-4686(01)00615-6","volume":"46","author":"Amatore C.","year":"2001","journal-title":"Electrochim. Acta"},{"key":"ref4\/cit4k","doi-asserted-by":"crossref","first-page":"92","DOI":"10.3998\/ark.5550190.0003.511","author":"Agenet N.","year":"2002","journal-title":"Arkivoc"},{"key":"ref4\/cit4l","doi-asserted-by":"crossref","first-page":"1569","DOI":"10.1021\/om049420d","volume":"24","author":"Amatore C.","year":"2005","journal-title":"Organometallics"},{"key":"ref5\/cit5a","doi-asserted-by":"crossref","first-page":"138","DOI":"10.1021\/om000712y","volume":"20","author":"Ross J.","year":"2001","journal-title":"Organometallics"},{"key":"ref5\/cit5b","doi-asserted-by":"crossref","first-page":"4900","DOI":"10.1002\/chem.200304895","volume":"9","author":"Ross J.","year":"2003","journal-title":"Chem.\u2014Eur. J."},{"key":"ref6\/cit6","doi-asserted-by":"crossref","first-page":"3920","DOI":"10.1021\/om00059a071","volume":"11","author":"Brookhart M.","year":"1992","journal-title":"Organometallics"},{"key":"ref7\/cit7a","doi-asserted-by":"crossref","first-page":"2597","DOI":"10.1021\/ja01638a093","volume":"76","author":"Winstein S.","year":"1954","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7b","unstructured":"bAt present it is unclear whether the approximately linear plots in Figure1are the early phases of a special salt effect (which should progressively inflect to a normal salt effect) or the linear portion of a, rather powerful, normal salt effect. Scheme3supports the former."},{"key":"ref8\/cit8","unstructured":"Crotyl acetate behaved analogously. SeeSupporting Information."},{"key":"ref9\/cit9","unstructured":"An analogous conclusion was made by Jutand and co-workers, for Pd catalysed allylic amination, but based on the kinetics of\n                      separate stoichiometric\n                      reactions (\n                      K\n                      OA\n                      and\n                      k\n                      Nu\n                      ), see reference4g."},{"key":"ref10\/cit10","unstructured":"Ligand association\/dissociation equilibria are not implicated: the bidentate dppf ligands (entries 11\u221213) give identical trends. Addition of 1 equiv ligand v (entry 5) resulted in severe attenuation of turnover rate."},{"key":"ref11\/cit11","doi-asserted-by":"crossref","first-page":"679","DOI":"10.1021\/om00083a006","volume":"3","author":"Akermark B.","year":"1984","journal-title":"Organometallics"},{"key":"ref12\/cit12a","doi-asserted-by":"crossref","first-page":"4942","DOI":"10.1021\/om700299b","volume":"26","author":"Nama D.","year":"2007","journal-title":"Organometallics"},{"key":"ref12\/cit12b","doi-asserted-by":"crossref","first-page":"261","DOI":"10.1016\/j.pnmrs.2006.09.001","volume":"49","author":"Pregosin P. S.","year":"2006","journal-title":"Prog. Nucl. Magn. Reson. Spectrosc."},{"key":"ref13\/cit13","unstructured":"The approximation d[\n                      3\n                      ]\/d\n                      t\n                      \u2248\n                      k\n                      L\n                      (1 +\n                      a\n                      [NaBAr\u2032F])[Pd\n                      tot\n                      ][\n                      2\n                      ] may only hold for low [NaBAr\u2032F] concentrations. See also ref7b."},{"key":"ref14\/cit14","unstructured":"(a) A mixture of\n                      1a\n                      and (nominally) (L)\n                      \n                        2\n                      \n                      Pd, was generated by reaction of [Pd\n                      2\n                      (allyl)\n                      2\n                      (OAc)\n                      2\n                      ] with i and v (L\/Pd = 2; \u221278\u219221 \u00b0C). For the analogous reaction with Cy\n                      3\n                      P, see: Yamamoto, T.; Saito, O.; Yamamoto, A.\n                      J. Am. Chem. Soc.\n                      1981\n                      ,\n                      103\n                      , 5600. The precatalyst mixture gave an identical\n                      k\n                      L\n                      value for\n                      1a\n                      \u2192\n                      3\n                      to that obtained with [\n                      4\n                      (L)\n                      2\n                      ][OTf]."},{"key":"ref14\/cit14b","unstructured":"b\n                      1\n                      H-NMR isotherm-derived equilibrium constants for NaBAr\u2032F + [\n                      4\n                      (L)\n                      2\n                      ][OTf] = NaOAc + [\n                      4\n                      (L)\n                      2\n                      ][BAr\u2032F] are\n                      K\n                      = 0.43 \u00b1 0.11 (i), and\n                      K\n                      = 193 \u00b1 147 (v), seeSupporting Information."},{"key":"ref15\/cit15","unstructured":"Reactions were substantially slower than in THF, seeSupporting Information, and proceeded with very approximately pseudo-zero-order kinetics, as might be expected from a steady-state concentration of [\n                      2\n                      ]."},{"key":"ref16\/cit16a","doi-asserted-by":"crossref","first-page":"1007","DOI":"10.1002\/adsc.200800006","volume":"350","author":"Ferretti A. C.","year":"2008","journal-title":"Adv. Synth. Catal."},{"key":"ref16\/cit16b","doi-asserted-by":"crossref","first-page":"7450","DOI":"10.1021\/ja062173f","volume":"128","author":"Blackmond D. G.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref16\/cit16c","doi-asserted-by":"crossref","first-page":"4289","DOI":"10.1002\/1521-3773(20011119)40:22<4289::AID-ANIE4289>3.0.CO;2-4","volume":"40","author":"Dominguez B.","year":"2001","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref17\/cit17","unstructured":"Further evidence for a change in ion-pairing in\n                      4\n                      \n                        +\n                      \n                      at the point of nucleophilic attack comes from competition between\n                      2\n                      (NaC(Me)E\n                      2\n                      ) and the less sterically hindered NaC(H)E\n                      2\n                      for limiting\n                      1a\n                      . Using more electron rich ligands, the selectivity for\n                      2\n                      could be approximately doubled by addition of 3.0 mM [NaBAr\u2032F], seeSupporting Information."},{"key":"ref18\/cit18","unstructured":"NaBAr\u2032F (3.0 mM) increased\n                      k\n                      \n                        1a\n                      \n                      \/\n                      k\n                      \n                        1b\n                      \n                      (0.15 \u2192 0.50) with [\n                      4\n                      (BINAP)][OTf]."},{"key":"ref19\/cit19a","doi-asserted-by":"crossref","first-page":"235","DOI":"10.1021\/ja9530782","volume":"118","author":"Trost B. M.","year":"1996","journal-title":"J. Am. Chem. Soc."},{"key":"ref19\/cit19b","doi-asserted-by":"crossref","first-page":"589","DOI":"10.1351\/pac200476030589","volume":"76","author":"Lloyd-Jones G. C.","year":"2004","journal-title":"Pure Appl. Chem."},{"key":"ref19\/cit19c","doi-asserted-by":"crossref","first-page":"2631","DOI":"10.1002\/adsc.200700315","volume":"349","author":"Svensen N.","year":"2007","journal-title":"Adv. Synth. Catal."},{"key":"ref20\/cit20","doi-asserted-by":"crossref","first-page":"11792","DOI":"10.1021\/ja036359f","volume":"125","author":"Clark T. P.","year":"2003","journal-title":"J. Am. Chem. Soc.,"},{"key":"ref21\/cit21","doi-asserted-by":"crossref","first-page":"663","DOI":"10.1016\/S0957-4166(00)86120-0","volume":"2","author":"Yamaguchi M.","year":"1991","journal-title":"Tetrahedron: Asymmetry"},{"key":"ref22\/cit22","unstructured":"Cation-stabilizing allylic substituents (for example, 1,1,3-Ar\n                      3\n                      ) may decrease\n                      k\n                      IR\n                      and\/or\n                      k\n                      Nu\n                      leading to a Pd-allyl species as resting state, see reference4a."},{"key":"ref23\/cit23","unstructured":"BAr\u2032F, or analogous \u201cnon-interactive\u201d (ref12) anions are often employed in systems propagating via contiguous cationic catalytic intermediates. The results herein show that BAr\u2032F can also be applied to catalytic cycles with neutral and cationic intermediates."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja806278e","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,5]],"date-time":"2023-03-05T21:13:49Z","timestamp":1678050829000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja806278e"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2008,10,8]]},"references-count":47,"journal-issue":{"issue":"44","published-print":{"date-parts":[[2008,11,5]]}},"alternative-id":["10.1021\/ja806278e"],"URL":"https:\/\/doi.org\/10.1021\/ja806278e","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2008,10,8]]}}}