{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,23]],"date-time":"2026-08-23T16:39:56Z","timestamp":1787503196076,"version":"build-2736575974"},"reference-count":125,"publisher":"Wiley","issue":"52","license":[{"start":{"date-parts":[[2023,8,10]],"date-time":"2023-08-10T00:00:00Z","timestamp":1691625600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100003725","name":"National Research Foundation of Korea","doi-asserted-by":"publisher","award":["NRF-2021R1A2C2093597"],"award-info":[{"award-number":["NRF-2021R1A2C2093597"]}],"id":[{"id":"10.13039\/501100003725","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2023,9,15]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>\n                    Chiral allylic amines are valuable building blocks for biologically important compounds and natural products. In this study, we present the use of cooperative cation\u2010binding catalysis as an efficient method for synthesizing chiral allylic amines. By utilizing a chiral oligoEG and potassium fluoride as a cation\u2010binding catalyst and base, respectively, a wide range of biologically relevant chiral 2\u2010nitroallylic amines are obtained with excellent enantioselectivities (up to &gt;99\u2009%\u2009\n                    <jats:italic>ee<\/jats:italic>\n                    ) through the organocatalytic asymmetric aza\u2010Henry\u2010like reaction of \u03b2\u2010monosubstituted and \u03b2,\u03b2\u2010disubstituted nitroalkenes with \u03b1\u2010amidosulfones as imine precursors. Extensive experimental studies are presented to illustrate plausible mechanisms. Preliminary use of a chiral 2\u2010nitroallylic amine as a Michael acceptor demonstrated its potential application for diversity\u2010oriented synthesis of bioactive compounds.\n                  <\/jats:p>","DOI":"10.1002\/chem.202301787","type":"journal-article","created":{"date-parts":[[2023,6,28]],"date-time":"2023-06-28T00:43:14Z","timestamp":1687912994000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":3,"title":["Enantioselective Synthesis of Chiral 2\u2010Nitroallylic Amines via Cooperative Cation\u2010Binding Catalysis"],"prefix":"10.1002","volume":"29","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3130-8967","authenticated-orcid":false,"given":"Jin Hyun","family":"Park","sequence":"first","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon 16419 Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9179-3197","authenticated-orcid":false,"given":"Pintu","family":"Maity","sequence":"additional","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon 16419 Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9899-4047","authenticated-orcid":false,"given":"Sushovan","family":"Paladhi","sequence":"additional","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon 16419 Korea"},{"name":"Department of Chemistry Thakur Prasad Singh (T.P.S.) College  Patna 800001 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7559-7919","authenticated-orcid":false,"given":"Han Yong","family":"Bae","sequence":"additional","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon 16419 Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9221-6789","authenticated-orcid":false,"given":"Choong Eui","family":"Song","sequence":"additional","affiliation":[{"name":"Department of Chemistry Sungkyunkwan University  Suwon 16419 Korea"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2023,8,10]]},"reference":[{"key":"e_1_2_9_1_1","unstructured":"For the selected 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amines:"},{"key":"e_1_2_9_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/B607537A"},{"key":"e_1_2_9_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol8016947"},{"key":"e_1_2_9_15_2","first-page":"3331","volume":"20","author":"Gnamm C.","year":"2008","journal-title":"Synthesis"},{"key":"e_1_2_9_16_1","unstructured":"For the selected reviews:"},{"key":"e_1_2_9_17_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960433d"},{"key":"e_1_2_9_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr970343o"},{"key":"e_1_2_9_19_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr020027w"},{"key":"e_1_2_9_20_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar100047x"},{"key":"e_1_2_9_21_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0sc00234h"},{"key":"e_1_2_9_22_2","doi-asserted-by":"publisher","DOI":"10.1039\/C1CS15104E"},{"key":"e_1_2_9_23_1","unstructured":"For the selected 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examples:"},{"key":"e_1_2_9_52_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010043d"},{"key":"e_1_2_9_53_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200604366"},{"key":"e_1_2_9_54_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.200700030"},{"key":"e_1_2_9_55_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr068057c"},{"key":"e_1_2_9_56_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar900271g"},{"key":"e_1_2_9_57_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900291g"},{"key":"e_1_2_9_58_2","doi-asserted-by":"publisher","DOI":"10.3390\/molecules15020709"},{"key":"e_1_2_9_59_2","doi-asserted-by":"publisher","DOI":"10.2533\/chimia.2012.913"},{"key":"e_1_2_9_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr300192h"},{"key":"e_1_2_9_61_1","unstructured":"For the selected examples:"},{"key":"e_1_2_9_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol9011458"},{"key":"e_1_2_9_63_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetasy.2010.05.027"},{"key":"e_1_2_9_64_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201201259"},{"key":"e_1_2_9_65_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4CC10261D"},{"key":"e_1_2_9_66_2","doi-asserted-by":"publisher","DOI":"10.1002\/adsc.201700787"},{"key":"e_1_2_9_67_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol702059x"},{"key":"e_1_2_9_68_1","unstructured":"It was proposed that these reactions proceed via the base-catalyzed aza-Henry reaction pathway involving the generation of the corresponding chiral vinylogous nitronate from the \u03b2 \u03b2-disubstituted nitroalkenes. See Ref.\u2005[13]c."},{"key":"e_1_2_9_69_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.1c00400"},{"key":"e_1_2_9_70_1","unstructured":"For the selected examples:"},{"key":"e_1_2_9_71_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200903903"},{"key":"e_1_2_9_72_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201004777"},{"key":"e_1_2_9_73_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms2216"},{"key":"e_1_2_9_74_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms8512"},{"key":"e_1_2_9_75_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201508127"},{"key":"e_1_2_9_76_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b10660"},{"key":"e_1_2_9_77_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201605637"},{"key":"e_1_2_9_78_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.7b02076"},{"key":"e_1_2_9_79_2","doi-asserted-by":"publisher","DOI":"10.1038\/ncomms14877"},{"key":"e_1_2_9_80_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.7b02628"},{"key":"e_1_2_9_81_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201703800"},{"key":"e_1_2_9_82_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b00547"},{"key":"e_1_2_9_83_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.8b02240"},{"key":"e_1_2_9_84_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.3c00825"},{"key":"e_1_2_9_85_1","unstructured":"According to the single-crystal structure of the complex of (R)-3\u2009cand KF the basicity of the fluoride can be reduced by hydrogen-bonding interactions (O\u2212H \u22c5\u22c5\u22c5 F) with the phenolic proton of the oligoEG catalysts. In addition to this reduced basicity the low coordination number of the fluoride would make the fluoride more nucleophilic. Consequently fluoride might act as a nucleophilic catalyst. See Ref.\u2005[17]b."},{"key":"e_1_2_9_86_1","unstructured":"No reactions were observed in the absence of either the catalyst or KF confirming the essential contributions of both the oligoEG catalyst and KF in cation-binding catalysis."},{"key":"e_1_2_9_87_1","unstructured":"When the excessive amounts of KF were used the isomerization of4\u2009a\u2032to4\u2009aoccurred. See Supporting Information for details."},{"key":"e_1_2_9_88_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja200820m"},{"key":"e_1_2_9_89_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr0406561"},{"key":"e_1_2_9_90_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aat4210"},{"key":"e_1_2_9_91_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja5075163"},{"key":"e_1_2_9_92_1","unstructured":"The configuration of aza-MBH-type products was determined to be (E) according to the X-ray analysis of4\u2009p. Moreover DFT calculation studies using Spartan \u203214 (ver. 1.1.4 EDF2 at 6-31G* level) show that the probability of aza-MBH-type products existing in (Z)-configuration is far less. The (E)-isomer is 6.94\u2005kcal\/mol more stable than the corresponding (Z)-isomer. See Supporting Information for details."},{"key":"e_1_2_9_93_1","unstructured":"Deposition Numbers2174218 (for4\u2009aa\u2032) and 2174213 (for4\u2009aq)contain the supplementary crystallographic data for this paper. These data can be provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum KarlsruheAccess Structures service."},{"key":"e_1_2_9_94_1","unstructured":"For the selected reviews of the enantiodivergent catalysis:"},{"key":"e_1_2_9_95_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b13340"},{"key":"e_1_2_9_96_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.7b00561"},{"key":"e_1_2_9_97_1","unstructured":"For the selected examples about theN-protecting-group directed stereodivergent catalysis:"},{"key":"e_1_2_9_98_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja0482435"},{"key":"e_1_2_9_99_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja057498v"},{"key":"e_1_2_9_100_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.joc.9b01501"},{"key":"e_1_2_9_101_2","doi-asserted-by":"publisher","DOI":"10.1039\/C9CC09151C"},{"key":"e_1_2_9_102_1","unstructured":"The nitroalkene1\u2009awas isomerized to the vinylogous nitronate1\u2009a\u2032under our catalytic condition. See Supporting Information for details."},{"key":"e_1_2_9_103_1","unstructured":"For the selected examples:"},{"key":"e_1_2_9_104_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b00685"},{"key":"e_1_2_9_105_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201611466"},{"key":"e_1_2_9_106_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c11815"},{"key":"e_1_2_9_107_1","unstructured":"For the selected examples ACE potent inhibitor:"},{"key":"e_1_2_9_108_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00148a024"},{"key":"e_1_2_9_109_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm950576c"},{"key":"e_1_2_9_110_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr950073e"},{"key":"e_1_2_9_111_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200504119"},{"key":"e_1_2_9_112_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.bbagen.2012.09.018"},{"key":"e_1_2_9_113_2","doi-asserted-by":"publisher","DOI":"10.1039\/C4NP00051J"},{"key":"e_1_2_9_114_1","unstructured":"\u00a0"},{"key":"e_1_2_9_115_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja074045c"},{"key":"e_1_2_9_116_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo800124v"},{"key":"e_1_2_9_117_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201202715"},{"key":"e_1_2_9_118_2","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b02769"},{"key":"e_1_2_9_119_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6b03217"},{"key":"e_1_2_9_120_2","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.201800476"},{"key":"e_1_2_9_121_1","unstructured":"\u00a0"},{"key":"e_1_2_9_122_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-2000-6232"},{"key":"e_1_2_9_123_2","doi-asserted-by":"publisher","DOI":"10.1039\/b517864a"},{"key":"e_1_2_9_124_2","doi-asserted-by":"publisher","DOI":"10.15227\/orgsyn.086.0011"},{"key":"e_1_2_9_125_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b12796"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202301787","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T17:54:04Z","timestamp":1760291644000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202301787"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2023,8,10]]},"references-count":125,"journal-issue":{"issue":"52","published-print":{"date-parts":[[2023,9,15]]}},"alternative-id":["10.1002\/chem.202301787"],"URL":"https:\/\/doi.org\/10.1002\/chem.202301787","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2023,8,10]]},"assertion":[{"value":"2023-06-04","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2023-08-10","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202301787"}}