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This transformation proceeds at room temperature in the presence of a quaternary ammonium catalyst and base to generate functionalized products containing an all\u2010carbon quaternary stereocentre. Quantum chemical calculations demonstrated that intramolecular general acid catalysis plays a key accelerating role through stabilization of developing charge in the transition state, and that the reaction is best described as a 5\u2010endo dig cyclization, rather than an anionic 6\u03c0 electrocyclization. Investigations employing chiral phase\u2010transfer catalysts have given promising selectivities to date.<\/jats:p>","DOI":"10.1002\/chem.201400192","type":"journal-article","created":{"date-parts":[[2014,2,12]],"date-time":"2014-02-12T08:41:00Z","timestamp":1392194460000},"page":"3005-3009","source":"Crossref","is-referenced-by-count":20,"title":["Phase\u2010Transfer\u2010Catalysed Synthesis of Pyrroloindolines and Pyridoindolines by a Hydrogen\u2010Bond\u2010Assisted Isocyanide Cyclization Cascade"],"prefix":"10.1002","volume":"20","author":[{"given":"Peter C.","family":"Knipe","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matija","family":"Gredi\u010dak","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Artiom","family":"Cernijenko","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Robert S.","family":"Paton","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Martin D.","family":"Smith","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2014,2,12]]},"reference":[{"key":"e_1_2_3_1_2","unstructured":"For reviews of pyrroloindolines see:"},{"key":"e_1_2_3_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/c005345g"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar050175j"},{"key":"e_1_2_3_4_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200700612"},{"key":"e_1_2_3_4_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200700612"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201001451"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1039\/b819925f"},{"key":"e_1_2_3_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar200004w"},{"key":"e_1_2_3_8_2","unstructured":"For reviews of pyridoindolines see Ref.\u2005[1\u2009a] and:"},{"key":"e_1_2_3_9_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.200801735"},{"key":"e_1_2_3_9_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.200801735"},{"key":"e_1_2_3_10_2","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201100014"},{"key":"e_1_2_3_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/ijch.201100024"},{"key":"e_1_2_3_12_2","doi-asserted-by":"publisher","DOI":"10.1039\/c0np00074d"},{"key":"e_1_2_3_13_2","doi-asserted-by":"crossref","first-page":"163","DOI":"10.1016\/S0735-8210(99)80025-9","volume-title":"Alkaloids: Chemical & Biological Perspectives, Vol.\u20052","author":"Anthoni U.","year":"1999"},{"key":"e_1_2_3_14_2","unstructured":"\u00a0"},{"key":"e_1_2_3_15_2","volume-title":"Basic and Clinical Pharmacology, 11th","author":"Katzung B. 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These data can be obtained free of charge from The Cambridge Crystallographic Data Centre viawww.ccdc.cam.ac.uk\/data_request\/cif."},{"key":"e_1_2_3_57_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206835"},{"key":"e_1_2_3_57_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206835"},{"key":"e_1_2_3_58_2","unstructured":"Due to instability the corresponding isocyanides were used in cyclization reactions without prior isolation. 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