{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,6]],"date-time":"2026-10-06T14:54:14Z","timestamp":1791298454803,"version":"4.1.0"},"reference-count":67,"publisher":"Wiley","issue":"32","license":[{"start":{"date-parts":[[2010,8,4]],"date-time":"2010-08-04T00:00:00Z","timestamp":1280880000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2010,8,23]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The diastereofacial selection in addition reactions to biased rigid systems can be modulated by the action of Lewis acids. As an example, the stereoselectivity of the nucleophilic addition of vinyl magnesium bromide (VMB) to cyclic nitrones in the presence of diethylaluminum chloride (DEAC) shows a strong dependence on the temperature and the carbon substituent adjacent at the reaction center; it is remarkable that whereas a high selectivity is obtained at higher temperatures, in the presence of DEAC, a trend to invert the stereochemical course of the reaction is observed at lower temperatures, provided the substituent at C3 of the pyrrolidine ring allows delivery of the vinyl moiety. This behavior and difference in selectivity is to be attributed to the high conformational barriers of the intermediate nitrone\uf8ffDEAC\uf8ffVMB complex. A clear inversion of the selectivity is observed at \u221278\u2009\u00b0C for the reaction of the nitrone protected as an <jats:italic>O<\/jats:italic>\u2010methyl derivative. The present study provides a rationalization for the stereocontrolled addition of nucleophiles to rigid systems (cyclic nitrones).<\/jats:p>","DOI":"10.1002\/chem.201001608","type":"journal-article","created":{"date-parts":[[2010,8,5]],"date-time":"2010-08-05T00:26:10Z","timestamp":1280967970000},"page":"9910-9919","source":"Crossref","is-referenced-by-count":36,"title":["Tunable Diastereoselection of Biased Rigid Systems by Lewis Acid Induced Conformational Effects: A Rationalization of the Vinylation of Cyclic Nitrones En Route to Polyhydroxylated Pyrrolidines"],"prefix":"10.1002","volume":"16","author":[{"given":"Ignacio","family":"Delso","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Eduardo","family":"Marca","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Vanni","family":"Mannucci","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Tom\u00e1s","family":"Tejero","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrea","family":"Goti","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Pedro","family":"Merino","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2010,8,17]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr980379w"},{"key":"e_1_2_6_2_2","unstructured":"\u00a0"},{"key":"e_1_2_6_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470517437"},{"key":"e_1_2_6_4_2","volume-title":"Iminosugars as Glycosidase Inhibitors: Nojirimycin and Beyond","year":"1998"},{"key":"e_1_2_6_5_2","unstructured":"\u00a0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1093\/glycob\/cwg090"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0957-4166(00)00113-0"},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.2174\/1568026033452492"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0031-9422(00)00451-9"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1081\/NCN-200027564"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0925-4439(02)00073-X"},{"key":"e_1_2_6_12_2","unstructured":"For reviews see:"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.2174\/092986708784049612"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr800464r"},{"key":"e_1_2_6_15_2","unstructured":"\u00a0"},{"key":"e_1_2_6_16_2","first-page":"485","author":"Revuelta 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Naturforsch. B"},{"key":"e_1_2_6_55_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(02)00057-1"},{"key":"e_1_2_6_56_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(01)00784-0"},{"key":"e_1_2_6_57_2","unstructured":"All critical points were fully optimized by analytical gradient method by using Gaussian\u200503 Revision E.01 M.\u2005J. Frisch G.\u2005W. Trucks H.\u2005B. Schlegel G.\u2005E. Scuseria M.\u2005A. Robb J.\u2005R. Cheeseman J.\u2005A. Montgomery \u2005Jr. T. Vreven K.\u2005N. Kudin J.\u2005C. Burant J.\u2005M. Millam S.\u2005S. Iyengar J. Tomasi V. Barone B. Mennucci M. Cossi G. Scalmani N. Rega G.\u2005A. Petersson H. Nakatsuji M. Hada M. Ehara K. Toyota R. Fukuda J. Hasegawa M. Ishida T. Nakajima Y. Honda O. Kitao H. Nakai M. Klene X. Li J.\u2005E. Knox H.\u2005P. Hratchian J.\u2005B. Cross V. Bakken C. Adamo J. Jaramillo R. Gomperts R.\u2005E. Stratmann O. Yazyev A.\u2005J. Austin R. Cammi C. Pomelli J.\u2005W. Ochterski P.\u2005Y. Ayala K. Morokuma G.\u2005A. Voth P. Salvador J.\u2005J. Dannenberg V.\u2005G. Zakrzewski S. Dapprich A.\u2005D. Daniels M.\u2005C. Strain O. Farkas D.\u2005K. Malick A.\u2005D. Rabuck K. Raghavachari J.\u2005B. Foresman J.\u2005V. Ortiz Q. Cui A.\u2005G. Baboul S. Clifford J. Cioslowski B.\u2005B. Stefanov G. Liu A. Liashenko P. Piskorz I. Komaromi R.\u2005L. Martin D.\u2005J. Fox T. Keith M.\u2005A. Al\u2010Laham C.\u2005Y. Peng A. Nanayakkara M. Challacombe P.\u2005M.\u2005W. Gill B. Johnson W. Chen M.\u2005W. Wong C. Gonzalez J.\u2005A. Pople Gaussian Inc. Wallingford CT 2004. For further details see the Supporting Information."},{"key":"e_1_2_6_58_2","unstructured":"Semiempirical conformational calculations were carried out at the PM3 level as implemented in the Gaussian\u200503 Rev\u2005E.01 package of programs (see Ref.\u2005[23]). This level is judged sufficient for considering steric and stereoelectronic factors governing the conformational properties of the studied complexes. The conformational analysis was carried out by rotating the N\uf8ffO bond in one degree steps. A total of 360 conformations were fully optimized. For details see the Supporting Information."},{"key":"e_1_2_6_59_2","unstructured":"For the structure of Grignard compounds in solution see:"},{"key":"e_1_2_6_60_2","doi-asserted-by":"publisher","DOI":"10.1021\/om900426h"},{"key":"e_1_2_6_61_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp9009788"},{"key":"e_1_2_6_62_2","doi-asserted-by":"publisher","DOI":"10.1021\/jp963999e"},{"key":"e_1_2_6_63_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.jorganchem.2009.10.016"},{"key":"e_1_2_6_64_2","unstructured":"Because the conformational barriers have been calculated at a semiempirical level they should be considered somewhat overestimated with respect to those calculated for the reaction at a DFT level. In any case the values remain within the same order of magnitude."},{"key":"e_1_2_6_65_2","unstructured":"The NMR spectra were obtained on Bruker Avance 500 by using a 5\u2005mm BB\u20101H\/13C dual probe. The spectra were recorded as solutions in [D8]THF by using commercial solutions of VMB and DEAC and at temperatures varying from 0 to \u221278\u2009\u00b0C. NMR spectra were recorded by using standard procedures."},{"key":"e_1_2_6_66_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00071-1"}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fchem.201001608","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.201001608","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T08:48:09Z","timestamp":1760258889000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.201001608"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2010,8,17]]},"references-count":67,"journal-issue":{"issue":"32","published-print":{"date-parts":[[2010,8,23]]}},"alternative-id":["10.1002\/chem.201001608"],"URL":"https:\/\/doi.org\/10.1002\/chem.201001608","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2010,8,17]]}}}