{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,7]],"date-time":"2026-10-07T20:59:43Z","timestamp":1791406783563,"version":"4.3.3"},"reference-count":53,"publisher":"American Chemical Society (ACS)","issue":"20","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Org. Lett."],"published-print":{"date-parts":[[2009,10,15]]},"DOI":"10.1021\/ol901820w","type":"journal-article","created":{"date-parts":[[2009,9,15]],"date-time":"2009-09-15T16:57:53Z","timestamp":1253033873000},"page":"4584-4587","source":"Crossref","is-referenced-by-count":118,"title":["Mechanistic Comparison between Pd-Catalyzed Ligand-Directed C\u2212H Chlorination and C\u2212H Acetoxylation"],"prefix":"10.1021","volume":"11","author":[{"given":"Kara J.","family":"Stowers","sequence":"first","affiliation":[{"name":"University of Michigan, Department of Chemistry, 930 North University, Ann Arbor, Michigan 48109-1055"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Melanie S.","family":"Sanford","sequence":"additional","affiliation":[{"name":"University of Michigan, Department of Chemistry, 930 North University, Ann Arbor, Michigan 48109-1055"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2009,9,15]]},"reference":[{"key":"ref1\/cit1","unstructured":"For reviews, see:"},{"key":"ref1\/cit1a","doi-asserted-by":"crossref","first-page":"2439","DOI":"10.1016\/j.tet.2005.11.027","volume":"62","author":"Dick A. R.","year":"2006","journal-title":"Tetrahedron"},{"key":"ref1\/cit1b","doi-asserted-by":"crossref","first-page":"3382","DOI":"10.1055\/s-2006-956468","author":"Daugulis O.","year":"2006","journal-title":"Synlett"},{"key":"ref1\/cit1c","doi-asserted-by":"crossref","first-page":"174","DOI":"10.1021\/cr0509760","volume":"107","author":"Alberico D.","year":"2007","journal-title":"Chem. Rev."},{"key":"ref1\/cit1d","first-page":"949","author":"Li B. J.","year":"2008","journal-title":"Synlett"},{"key":"ref1\/cit1e","doi-asserted-by":"crossref","first-page":"5094","DOI":"10.1002\/anie.200806273","volume":"48","author":"Chen X.","year":"2009","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref2\/cit2","unstructured":"For examples, see:"},{"key":"ref2\/cit2a","doi-asserted-by":"crossref","first-page":"9542","DOI":"10.1021\/ja046831c","volume":"126","author":"Desai L. V.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"7420","DOI":"10.1002\/anie.200502767","volume":"44","author":"Giri R.","year":"2005","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref2\/cit2c","doi-asserted-by":"crossref","first-page":"3391","DOI":"10.1021\/ol061389j","volume":"8","author":"Reddy B. V. S.","year":"2006","journal-title":"Org. Lett."},{"key":"ref3\/cit3","unstructured":"For examples, see:"},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"2300","DOI":"10.1021\/ja031543m","volume":"126","author":"Dick A. R.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3b","doi-asserted-by":"crossref","first-page":"2112","DOI":"10.1002\/anie.200462884","volume":"44","author":"Giri R.","year":"2005","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref3\/cit3c","doi-asserted-by":"crossref","first-page":"11483","DOI":"10.1016\/j.tet.2006.06.075","volume":"62","author":"Kalyani D.","year":"2006","journal-title":"Tetrahedron"},{"key":"ref3\/cit3d","doi-asserted-by":"crossref","first-page":"7134","DOI":"10.1021\/ja061943k","volume":"128","author":"Hull K. L.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3e","doi-asserted-by":"crossref","first-page":"7416","DOI":"10.1021\/ja060232j","volume":"128","author":"Wan X.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref3\/cit3f","doi-asserted-by":"crossref","first-page":"7520","DOI":"10.1021\/ja901352k","volume":"131","author":"Wang X.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4","unstructured":"For examples, see:"},{"key":"ref4\/cit4a","doi-asserted-by":"crossref","first-page":"9048","DOI":"10.1021\/ja062856v","volume":"128","author":"Thu H. Y.","year":"2006","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4b","doi-asserted-by":"crossref","first-page":"16184","DOI":"10.1021\/ja806543s","volume":"130","author":"Jordon-Hore J. A.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref4\/cit4c","doi-asserted-by":"crossref","first-page":"10806","DOI":"10.1021\/ja904709b","volume":"131","author":"Mei T. S.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref5\/cit5","doi-asserted-by":"crossref","first-page":"3466","DOI":"10.1021\/ja900200g","volume":"131","author":"Zhao X.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref6\/cit6","doi-asserted-by":"crossref","first-page":"9886","DOI":"10.1021\/ja903573p","volume":"131","author":"Wasa M.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7a","doi-asserted-by":"crossref","first-page":"14047","DOI":"10.1021\/ja065718e","volume":"128","author":"Hull K. L.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7b","doi-asserted-by":"crossref","first-page":"13285","DOI":"10.1021\/ja8045519","volume":"130","author":"Desai L. V.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7c","doi-asserted-by":"crossref","first-page":"9651","DOI":"10.1021\/ja901952h","volume":"131","author":"Hull K. L.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7d","doi-asserted-by":"crossref","first-page":"10974","DOI":"10.1021\/ja9014474","volume":"131","author":"Racowski J. M.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref7\/cit7e","doi-asserted-by":"crossref","first-page":"11234","DOI":"10.1021\/ja904116k","volume":"131","author":"Deprez N. R.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref8\/cit8a","doi-asserted-by":"crossref","first-page":"9879","DOI":"10.1021\/ja071845e","volume":"129","author":"Chiong H. A.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref8\/cit8b","doi-asserted-by":"crossref","first-page":"6979","DOI":"10.1016\/j.tet.2008.03.026","volume":"64","author":"Li J. J.","year":"2008","journal-title":"Tetrahedron"},{"key":"ref8\/cit8c","doi-asserted-by":"crossref","first-page":"302","DOI":"10.1038\/nchem.246","volume":"1","author":"Powers D. C.","year":"2009","journal-title":"Nat. Chem."},{"key":"ref9\/cit9","unstructured":"The identity of the ancillary ligands in the catalytic intermediates is not known; as a result, these ligands are represented as sticks."},{"key":"ref10\/cit10","doi-asserted-by":"crossref","first-page":"15142","DOI":"10.1021\/ja077866q","volume":"129","author":"Whitfield S. R.","year":"2007","journal-title":"J. Am. Chem. Soc."},{"key":"ref11\/cit11","unstructured":"2-Benzylpyridines were used in a previous mechanistic study of Pd-catalyzed C\u2212H acetoxylation (ref7b). However, these substrates reacted with NCS to form undesired benzylic chlorination side products."},{"key":"ref12\/cit12","unstructured":"The OAc is presumably derived from the Pd(OAc)2catalyst."},{"key":"ref13\/cit13","unstructured":"The kinetic studies were run at different concentrations (0.024 M for chlorination versus 0.048 M for acetoxylation) because the data for each reaction was significantly more reproducible under these conditions. However, the same kinetic orders and analogous Hammett trends were observed for chlorination at 0.048 M. See theSupporting Information."},{"key":"ref14\/cit14","unstructured":"Intermolecular primary KIE values between 3.58 and 1.85 were observed in the Pd-catalyzed C\u2212H acetoxylation of 2-benzylpyridines (ref7b)."},{"key":"ref15\/cit15","unstructured":"Interpretation of the Hammett data is somewhat complicated by the conjugated biaryl system in1, since substitution of Y and Z can influence the electronics of both the pyridine (which binds to the metal) and theortho-C\u2212H bond (which undergoes activation). We note that the observed \u03c1 value for C\u2212H acetoxylation (+0.89 in MeCN) is reasonably similar to that reported for benzylpyridines (+1.40 in benzene, ref7b), where the pyridine and aryl group are electronically isolated. Thus, we hypothesize that the effect observed here is predominantly due to pyridine electronics."},{"key":"ref16\/cit16","unstructured":"For examples, see:"},{"key":"ref16\/cit16a","doi-asserted-by":"crossref","first-page":"117","DOI":"10.1016\/S0022-328X(00)82943-5","volume":"205","author":"Deeming A. J.","year":"1981","journal-title":"J. Organomet. Chem."},{"key":"ref16\/cit16b","doi-asserted-by":"crossref","first-page":"2629","DOI":"10.1039\/dt9850002629","author":"Ryabov A. D.","year":"1985","journal-title":"J. Chem. Soc., Dalton Trans."},{"key":"ref16\/cit16c","doi-asserted-by":"crossref","first-page":"403","DOI":"10.1021\/cr00100a004","volume":"90","author":"Ryabov A. D.","year":"1990","journal-title":"Chem. Rev."},{"key":"ref17\/cit17","doi-asserted-by":"crossref","first-page":"192","DOI":"10.1016\/S0020-1693(02)01148-9","volume":"340","author":"Kurzeev S. A.","year":"2002","journal-title":"Inorg. Chim. Acta"},{"key":"ref18\/cit18","doi-asserted-by":"crossref","first-page":"39","DOI":"10.1080\/02603590701394766","volume":"28","author":"Vicente J.","year":"2007","journal-title":"Comments Inorg. Chem."},{"key":"ref19\/cit19","unstructured":"For examples of cyclometalation mechanisms analogous to path a, see ref16cas well as:"},{"key":"ref19\/cit19a","first-page":"2711","volume":"24","author":"Yatsimirsky A. K.","year":"1979","journal-title":"Zh. Neorg. Khim."},{"key":"ref19\/cit19b","doi-asserted-by":"crossref","first-page":"619","DOI":"10.1246\/bcsj.71.619","volume":"71","author":"Yagyu T.","year":"1998","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref19\/cit19c","doi-asserted-by":"crossref","first-page":"1857","DOI":"10.1246\/bcsj.71.1857","volume":"71","author":"Yagyu T.","year":"1998","journal-title":"Bull. Chem. Soc. Jpn."},{"key":"ref19\/cit19d","doi-asserted-by":"crossref","first-page":"2341","DOI":"10.1002\/1521-3765(20010601)7:11<2341::AID-CHEM23410>3.0.CO;2-S","volume":"7","author":"Martin-Matute B.","year":"2001","journal-title":"Chem.\u2014Eur. J."},{"key":"ref20\/cit20","unstructured":"For examples of cyclometalation mechanisms analogous to path b, see:"},{"key":"ref20\/cit20a","doi-asserted-by":"crossref","first-page":"1831","DOI":"10.1021\/om00029a045","volume":"12","author":"Alsters P. L.","year":"1993","journal-title":"Organometallics"},{"key":"ref20\/cit20b","doi-asserted-by":"crossref","first-page":"2561","DOI":"10.1002\/ejic.200600320","author":"Otto S.","year":"2006","journal-title":"Eur. J. Inorg. Chem."},{"key":"ref21\/cit21","unstructured":"An alternative explanation would be that the catalyst resting state is a mixture of monomeric and dimeric Pd species (see ref8cfor a similar proposal). However, we believe that this is unlikely, as literature precedent suggests that the reaction between a large excess of1and Pd(OAc)2to form Pd(OAc)2(1)2should to be fast and essentially quantitative, particularly at 70 \u00b0C. See refs16\u221218."}],"container-title":["Organic Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ol901820w","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,9]],"date-time":"2023-03-09T15:41:57Z","timestamp":1678376517000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ol901820w"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,9,15]]},"references-count":53,"journal-issue":{"issue":"20","published-print":{"date-parts":[[2009,10,15]]}},"alternative-id":["10.1021\/ol901820w"],"URL":"https:\/\/doi.org\/10.1021\/ol901820w","relation":{},"ISSN":["1523-7060","1523-7052"],"issn-type":[{"value":"1523-7060","type":"print"},{"value":"1523-7052","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,9,15]]}}}