{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,17]],"date-time":"2026-10-17T18:40:31Z","timestamp":1792262431210,"version":"4.4.0"},"reference-count":66,"publisher":"Wiley","issue":"43","license":[{"start":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T00:00:00Z","timestamp":1788220800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T00:00:00Z","timestamp":1788220800000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22571199"],"award-info":[{"award-number":["22571199"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22222107"],"award-info":[{"award-number":["22222107"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012600","name":"ShanghaiTech University","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100012600","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,10,19]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>Inherently chiral calix[4]arenes (ICCs) are chiral macrocyclic compounds whose chirality arises from the asymmetric distribution of substituents in their rigid cone conformations. Although inherent chirality in these systems has long been recognized, the enantioselective synthesis of these structurally intriguing frameworks, especially non\u2010meta\u2010type ICCs, remains underexplored. In this work, we report a versatile method for the asymmetric synthesis of both ABCD\u2010 and ABCC\u2010type ICCs via an enantioselective desymmetrization strategy. Two classes of diamino\u2010substituted prochiral calix[4]arenes were efficiently desymmetrized through chiral phosphoric acid\u2010catalyzed reductive amination with various aldehydes, tolerating a broad range of upper\u2010rim substitutions and affording both ABCD\u2010 and ABCC\u2010type ICCs bearing diverse functional groups with high enantioselectivities. Control experiments suggest that the reaction proceeds via sequential enantioselective desymmetrization and kinetic resolution, with reduction of the imine identified as the enantiodetermining step. Various derivatizations of the ICC products were also performed, including three notable examples involving dimerization of ICCs. Moreover, we demonstrate that combining these asymmetric synthetic and derivatization methods could enable the asymmetric synthesis of all six possible stereoisomers of the ABCD\u2010type ICCs. Furthermore, incorporation of fluorophore groups into these inherently chiral frameworks furnished ICC derivatives with promising photophysical and chiroptical properties, further underscoring the potential of this methodology.<\/jats:p>","DOI":"10.1002\/anie.7517064","type":"journal-article","created":{"date-parts":[[2026,9,1]],"date-time":"2026-09-01T10:38:48Z","timestamp":1788259128000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Catalytic Enantioselective Synthesis of Upper\u2010rim\u2010Functionalized Inherently Chiral Calix[4]arenes Through Desymmetrizing Reductive Amination"],"prefix":"10.1002","volume":"65","author":[{"given":"Mengyao","family":"Yuan","sequence":"first","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"},{"name":"Lingang Laboratory  Shanghai China"},{"name":"State Key Laboratory of Elemento\u2010Organic Chemistry Nankai University  Tianjin China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0003-3551-9865","authenticated-orcid":false,"given":"Xi","family":"Xiang","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"},{"name":"State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wansen","family":"Xie","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuheng","family":"Ma","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0001-1820-7494","authenticated-orcid":false,"given":"Huanchao","family":"Gu","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7598-0275","authenticated-orcid":false,"given":"Houchao","family":"Tao","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Discovery and Utilization of Functional Components in Traditional Chinese Medicine Innovation Research Institute of Traditional Chinese Medicine, Shanghai University of Traditional Chinese Medicine Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0756-0671","authenticated-orcid":false,"given":"Xiaoyu","family":"Yang","sequence":"additional","affiliation":[{"name":"School of Physical Science and Technology ShanghaiTech University  Shanghai China"},{"name":"State Key Laboratory of Elemento\u2010Organic Chemistry Nankai University  Tianjin China"},{"name":"State Key Laboratory of Advanced Medical Materials and Devices ShanghaiTech University  Shanghai China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,1]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-319-31867-7"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar500009g"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1039\/C2CS35233H"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00605"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr8002196"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202200532"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.3390\/ijms12010429"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1007\/s10847\u2010011\u20109935\u20104"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1007\/BF00708972"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201703367"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2005.06.015"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol071249p"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.14.117"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.trechm.2025.06.007"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202502247"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/tcr.202400237"},{"key":"e_1_2_8_18_1","article-title":"Inherently Chiral Macrocycles: Catalytic Asymmetric Synthesis and Properties","volume":"25","author":"Tong S.","year":"2025","journal-title":"Accounts of Chemical Research"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetasy.2009.01.017"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c05369"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c10606"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2SC06234H"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201052133\u20108"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202412459"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.70414"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202520283"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5SC10040B"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.6c00211"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202407752"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202410628"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5c08274"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201054380\u20101"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010025\u201059221\u20103"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.orglett.5c04041"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cclet.2025.112157"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1039\/D4GC02877E"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0040\u20104039(97)10865\u20106"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202518659"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-025-59781-4"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1039\/D5QO01509J"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202300738"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/cjoc.202400243"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202515020"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2025.102694"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200353240"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja0491533"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/cr5001496"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.3762\/bjoc.21.145"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cs15268h"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/ejoc.202100894"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200503062"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/ol0515964"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201310562"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201606063"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6b06009"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1039\/D6SC03274E"},{"key":"e_1_2_8_57_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.checat.2023.100827"},{"key":"e_1_2_8_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.6c06853"},{"key":"e_1_2_8_59_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.chempr.2024.06.012"},{"key":"e_1_2_8_60_1","unstructured":"Deposition Numbers 2554407 (8a) 2554408 (9a) and 2554410 (18a) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service."},{"key":"e_1_2_8_61_1","doi-asserted-by":"publisher","DOI":"10.1002\/ajoc.202100091"},{"key":"e_1_2_8_62_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja800793t"},{"key":"e_1_2_8_63_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.6b00052"},{"key":"e_1_2_8_64_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.tetlet.2019.151232"},{"key":"e_1_2_8_65_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201408193"},{"key":"e_1_2_8_66_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202210542"},{"key":"e_1_2_8_67_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202421060"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.7517064","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.7517064","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.7517064","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,17]],"date-time":"2026-10-17T17:41:14Z","timestamp":1792258874000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.7517064"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,1]]},"references-count":66,"journal-issue":{"issue":"43","published-print":{"date-parts":[[2026,10,19]]}},"alternative-id":["10.1002\/anie.7517064"],"URL":"https:\/\/doi.org\/10.1002\/anie.7517064","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,1]]},"assertion":[{"value":"2026-06-07","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-08-20","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-09-01","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e7517064"}}