{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,18]],"date-time":"2026-08-18T10:03:34Z","timestamp":1787047414605,"version":"build-2736575974"},"reference-count":80,"publisher":"Wiley","issue":"47","license":[{"start":{"date-parts":[[2017,8,2]],"date-time":"2017-08-02T00:00:00Z","timestamp":1501632000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100001412","name":"Council of Scientific and Industrial Research","doi-asserted-by":"publisher","award":["02(0013)\/11\/EMR-II"],"award-info":[{"award-number":["02(0013)\/11\/EMR-II"]}],"id":[{"id":"10.13039\/501100001412","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2017,8,22]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>A catalytic enantioselective construction of vicinal stereocenters is reported. The reaction takes advantage of thiourea\u2010catalyzed intramolecular nitronate addition onto \u03b1,\u03b2\u2010unsaturated ester to afford exceptional levels of enantioselectivity (up to 97\u2009% <jats:italic>ee<\/jats:italic>) with moderate diastereoselectivity (up to 4:1). Using this method, a cross\u2010conjugated ester was synthesized in few steps, from which a 6\u2010<jats:italic>endo<\/jats:italic>\u2010<jats:italic>trig<\/jats:italic> cyclisation led to the formation of all required functionalities for total syntheses of ergot alkaloids. The strategy not only offers first total syntheses of ergot alkaloids, festuclavine (<jats:bold>1\u2009c<\/jats:bold>), and pyroclavine (<jats:bold>1\u2009e<\/jats:bold>), and but also an efficient and general approach to other congeners such as, lysergol (<jats:bold>1\u2009b<\/jats:bold>), and isolysergol (<jats:bold>1\u2009d<\/jats:bold>).<\/jats:p>","DOI":"10.1002\/chem.201702459","type":"journal-article","created":{"date-parts":[[2017,7,7]],"date-time":"2017-07-07T09:49:46Z","timestamp":1499420986000},"page":"11234-11238","source":"Crossref","is-referenced-by-count":30,"title":["Total Syntheses of Pyroclavine, Festuclavine, Lysergol, and Isolysergol via a Catalytic Asymmetric Nitro\u2010Michael Reaction"],"prefix":"10.1002","volume":"23","author":[{"given":"Subhajit","family":"Bhunia","sequence":"first","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research Bhopal  231, Academic Building II, Indore By-Pass Road Bhopal 462 066 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Saikat","family":"Chaudhuri","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research Bhopal  231, Academic Building II, Indore By-Pass Road Bhopal 462 066 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5295-9756","authenticated-orcid":false,"given":"Alakesh","family":"Bisai","sequence":"additional","affiliation":[{"name":"Department of Chemistry Indian Institute of Science Education and Research Bhopal  231, Academic Building II, Indore By-Pass Road Bhopal 462 066 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2017,8,2]]},"reference":[{"key":"e_1_2_2_1_1","unstructured":"\u00a0"},{"key":"e_1_2_2_2_2","first-page":"45","volume-title":"The Alkaloids, Vol.\u200563","author":"Schardl C. 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Interestingly minor product (S R)-6\u2009acan be converted to (S S)-6\u2009ain 72\u2009% yield by epimerization in the presence of 6\u2005equiv of Et3N in refluxing toluene thereby increasing overall efficiency of our strategy."},{"key":"e_1_2_2_69_1","unstructured":"Absolute stereochemistry of major diastereomer (S S)-6\u2009bwas established by total synthesis of unnatural (+)-festuclavine (ent-1\u2009c) and (+)-pyroclavine (ent-1\u2009e) (please see Scheme below)."},{"key":"e_1_2_2_70_1","unstructured":"Catalytic intramolecular Michael reaction of compound11\u2009b(1\u2005g scale) using 5\u2005mol\u2009% thiourea catalystL3afforded (R R)-6\u2009bin 85\u2009% yield (\u22487 d) with 97\u2009%ee(d.r.=3.6:1)."},{"key":"e_1_2_2_71_1","unstructured":"Aldehyde28could be an advanced intermediate for the synthesis of ergot alkaloids via a reductive cyclization. However an attempt towards this from diol27lead to the formation of unexpected tetracyclic compound29in 75\u2009% yield as sole product (See Supporting Information for plausible mechanism)."},{"key":"e_1_2_2_72_1","doi-asserted-by":"publisher","DOI":"10.1021\/jo801761f"},{"key":"e_1_2_2_73_1","unstructured":"Diastereomeric mixture of methylester analogue of23and24is known to produce lysergic acid via one pot saponification and tosyl deprotection reflux condition for reference see 3\u2005L."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201702459","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201702459","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T10:09:38Z","timestamp":1760263778000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201702459"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2017,8,2]]},"references-count":80,"journal-issue":{"issue":"47","published-print":{"date-parts":[[2017,8,22]]}},"alternative-id":["10.1002\/chem.201702459"],"URL":"https:\/\/doi.org\/10.1002\/chem.201702459","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2017,8,2]]}}}