{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T06:56:07Z","timestamp":1792652167367,"version":"4.5.0"},"reference-count":54,"publisher":"American Chemical Society (ACS)","issue":"31","content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["J. Am. Chem. 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E.","year":"1994"},{"key":"ref2\/cit2a","volume-title":"Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications","author":"Filler R.","year":"1993"},{"key":"ref2\/cit2b","doi-asserted-by":"crossref","first-page":"1881","DOI":"10.1126\/science.1131943","volume":"317","author":"M\u00fcller K.","year":"2007","journal-title":"Science"},{"key":"ref2\/cit2c","doi-asserted-by":"crossref","first-page":"320","DOI":"10.1039\/B610213C","volume":"37","author":"Purser S.","year":"2008","journal-title":"Chem. Soc. Rev."},{"key":"ref2\/cit2d","doi-asserted-by":"crossref","first-page":"4359","DOI":"10.1021\/jm800219f","volume":"51","author":"Hagmann W. K.","year":"2008","journal-title":"J. Med. Chem."},{"key":"ref3\/cit3","unstructured":"For a review of strategies for trifluoromethylation, see:"},{"key":"ref3\/cit3a","doi-asserted-by":"crossref","first-page":"975","DOI":"10.1016\/j.jfluchem.2007.04.026","volume":"128","author":"Ma J.-A.","year":"2007","journal-title":"J. Fluorine Chem."},{"key":"ref4\/cit4","unstructured":"For reviews of asymmetric trifluoromethylations, see:"},{"key":"ref4\/cit4a","first-page":"PR1\u2212PR43","volume":"108","author":"Ma J.-A.","year":"2008","journal-title":"Chem. Rev."},{"key":"ref4\/cit4b","doi-asserted-by":"crossref","first-page":"2633","DOI":"10.1016\/j.tetasy.2008.11.011","volume":"19","author":"Shibata N.","year":"2008","journal-title":"Tetrahedron: Asymmetry"},{"key":"ref4\/cit4c","doi-asserted-by":"crossref","first-page":"891","DOI":"10.1002\/ejoc.200600643","author":"Billard T.","year":"2007","journal-title":"Eur. J. Org. 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P.","year":"2000","journal-title":"Tetrahedron"},{"key":"ref5\/cit5e","doi-asserted-by":"crossref","first-page":"4271","DOI":"10.1021\/ol016933x","volume":"3","author":"Ait-Mohand S.","year":"2001","journal-title":"Org. Lett."},{"key":"ref6\/cit6","unstructured":"For seminal contributions towards the electrophilic or radical trifluoromethylation of enamines, enolates, and other carbonyl derivatives, see:"},{"key":"ref6\/cit6a","doi-asserted-by":"crossref","first-page":"2031","DOI":"10.1016\/S0040-4039(00)75286-5","volume":"16","author":"Cantacuz\u00e8ne D.","year":"1975","journal-title":"Tetrahedron Lett."},{"key":"ref6\/cit6b","doi-asserted-by":"crossref","first-page":"6391","DOI":"10.1016\/S0040-4039(00)97073-4","volume":"31","author":"Miura K.","year":"1990","journal-title":"Tetrahedron Lett."},{"key":"ref6\/cit6c","doi-asserted-by":"crossref","first-page":"2156","DOI":"10.1021\/ja00059a009","volume":"115","author":"Umemoto T.","year":"1993","journal-title":"J. Am. Chem. 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A.","year":"2008","journal-title":"Science"},{"key":"ref10\/cit10","unstructured":"For recent examples of photoredox catalysis applications in organic synthesis, see:"},{"key":"ref10\/cit10a","doi-asserted-by":"crossref","first-page":"12886","DOI":"10.1021\/ja805387f","volume":"130","author":"Ischay M. A.","year":"2008","journal-title":"J. Am. Chem. Soc."},{"key":"ref10\/cit10b","doi-asserted-by":"crossref","first-page":"166","DOI":"10.1246\/cl.2009.166","volume":"38","author":"Koike T.","year":"2009","journal-title":"Chem. Lett."},{"key":"ref10\/cit10c","doi-asserted-by":"crossref","first-page":"8756","DOI":"10.1021\/ja9033582","volume":"131","author":"Narayanam J. M. R.","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"ref10\/cit10d","doi-asserted-by":"crossref","unstructured":"dM\u00fcller, C., Bauer, A., and Bach, T.Angew. Chem., Int. Ed.2009,48,DOI: 10.1002\/anie.200901603.","DOI":"10.1002\/anie.200901603"},{"key":"ref10\/cit10e","doi-asserted-by":"crossref","unstructured":"eDu, J. and Yoon, T. P.J. Am. Chem. Soc.2009,131,DOI: 10.1021\/ja903732v.","DOI":"10.1021\/ja903732v"},{"key":"ref11\/cit11","unstructured":"Although Ir(ppy)2(dtb-bpy)PF61was optimal for this transformation, commercially available Ru(bpy)3Cl2could also be used to afford the desired products in slightly diminished yields and enantioselectivities (Table1, entry 5).1is available in a single step from commercially available [Ir(ppy)2Cl]2(Sigma-Aldrich, CAS-No 92220-65-0). See ref 12."},{"key":"ref12\/cit12","unstructured":"For synthesis and photophysical properties of Ir(ppy)2(dtb-bpy)PF61, see:"},{"key":"ref12\/cit12a","doi-asserted-by":"crossref","first-page":"2763","DOI":"10.1021\/ja0345221","volume":"126","author":"Slinker J. D.","year":"2004","journal-title":"J. Am. Chem. Soc."},{"key":"ref12\/cit12b","doi-asserted-by":"crossref","first-page":"143","DOI":"10.1007\/128_2007_131","volume":"281","author":"Flamigni L.","year":"2007","journal-title":"Top. Curr. Chem."},{"key":"ref13\/cit13","unstructured":"Fluorescence quenching experiments using preformed enamine4(R = Bn) confirmed quenching of *Ir(ppy)2(dtb-bpy)PF6, Stern\u2212Volmer constant = 185; seeSupporting Informationfor details."},{"key":"ref14\/cit14a","doi-asserted-by":"crossref","first-page":"3509","DOI":"10.1021\/ja00165a040","volume":"112","author":"Andrieux C. P.","year":"1990","journal-title":"J. Am. Chem. Soc."},{"key":"ref14\/cit14b","doi-asserted-by":"crossref","first-page":"1583","DOI":"10.1039\/b000474j","author":"Bonesi S. M.","year":"2000","journal-title":"J. Chem. Soc., Perkin Trans. 2"},{"key":"ref15\/cit15","doi-asserted-by":"crossref","first-page":"189","DOI":"10.1016\/0009-2614(86)80542-5","volume":"131","author":"Wayner D. D. M.","year":"1986","journal-title":"Chem. Phys. Lett."},{"key":"ref16\/cit16","unstructured":"Performed using B3LYP\/6-311+G(2d,p)\/\/B3LYP\/6-31G(d). See ref 9."},{"key":"ref17\/cit17","unstructured":"We have recently shown the disruption of a postreaction racemization pathway via design of catalyst2(versus catalyst10); see:"},{"key":"ref17\/cit17a","doi-asserted-by":"crossref","first-page":"5121","DOI":"10.1002\/anie.200901855","volume":"48","author":"Amatore M.","year":"2009","journal-title":"Angew. Chem., Int. Ed."},{"key":"ref18\/cit18","unstructured":"The transformation does not proceed in the absence of the amine catalyst. The addition of 2,6-lutidine is necessary to remove hydroiodic acid that is formed during the reaction. Rapid racemization of the \u03b1-CF3formyl adduct was observed at room temperature but not at \u221220 \u00b0C."},{"key":"ref19\/cit19","unstructured":"Lower reaction efficiency appears to lead to lower enantiopurity as the product is exposed to unconsumed base (i.e., Table1, entry 5, catalyst9)."},{"key":"ref20\/cit20","unstructured":"A hitherto unreported amine catalyst11was employed in entry 7 (Table2); seeSupporting Information."},{"key":"ref21\/cit21","unstructured":"Efficient construction of a benzylic CF3bond on the unsubstituted parent compound, phenylacetaldehyde, is also attainable (cf. 89%19F NMR yield); however facile postreaction racemization is observed."},{"key":"ref22\/cit22","unstructured":"General Procedure for the Enantioselective \u03b1-Trifluoromethylation of Aldehydes: To a dry test tube were added organocatalyst2(0.20 equiv), photocatalyst1(0.005 equiv), and DMF (0.3 M). The resultant yellow solution was degassed by alternating vacuum evacuation\/argon backfill (\u00d73) at \u221278 \u00b0C before addition of CF3I (\u223c8 equiv), followed by aldehyde (0.76 mmol, 1.0 equiv) and 2,6-lutidine (1.1 equiv). The reaction vessel was placed near a 26 W compact fluorescent light bulb in a \u221220 \u00b0C bath for 7.5\u22128 h. Upon reaction completion, the \u03b1-trifluoromethyl aldehydes were typically reduced in situ with NaBH4(10 equiv) in CH2Cl2and MeOH to afford \u03b2-trifluoromethyl alcohols in high yield and enantioselectivity."}],"container-title":["Journal of the American Chemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/ja9053338","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,3,7]],"date-time":"2023-03-07T20:20:35Z","timestamp":1678220435000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/doi\/10.1021\/ja9053338"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2009,7,20]]},"references-count":54,"journal-issue":{"issue":"31","published-print":{"date-parts":[[2009,8,12]]}},"alternative-id":["10.1021\/ja9053338"],"URL":"https:\/\/doi.org\/10.1021\/ja9053338","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2009,7,20]]}}}