{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,19]],"date-time":"2025-10-19T06:02:20Z","timestamp":1760853740375},"reference-count":20,"publisher":"Wiley","issue":"1","license":[{"start":{"date-parts":[[2014,1,17]],"date-time":"2014-01-17T00:00:00Z","timestamp":1389916800000},"content-version":"vor","delay-in-days":16,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Helvetica Chimica Acta"],"published-print":{"date-parts":[[2014,1]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The classical synthesis, followed by purification of the steroidal <jats:italic>A<\/jats:italic>\u2010ring \u0394<jats:sup>1<\/jats:sup>\u2010olefin, 5<jats:italic>\u03b1<\/jats:italic>\u2010androst\u20101\u2010en\u201017\u2010one (<jats:bold>5<\/jats:bold>), from the \u0394<jats:sup>1<\/jats:sup>\u20103\u2010keto enone, (5<jats:italic>\u03b1<\/jats:italic>,17<jats:italic>\u03b2<\/jats:italic>)\u20103\u2010oxo\u20105\u2010androst\u20101\u2010en\u201017\u2010yl acetate (<jats:bold>1<\/jats:bold>), through a strategy involving the reaction of \u0394<jats:sup>1<\/jats:sup>\u20103\u2010hydroxy allylic alcohol, 3<jats:italic>\u03b2<\/jats:italic>\u2010hydroxy\u20105<jats:italic>\u03b1<\/jats:italic>\u2010androst\u20101\u2010en\u201017<jats:italic>\u03b2<\/jats:italic>\u2010yl acetate (<jats:bold>2<\/jats:bold>), with SOCl<jats:sub>2<\/jats:sub>, was revisited in order to prepare and biologically evaluate <jats:bold>5<\/jats:bold> as aromatase inhibitor for breast cancer treatment. Surprisingly, the followed strategy also afforded the isomeric \u0394<jats:sup>2<\/jats:sup>\u2010olefin <jats:bold>6<\/jats:bold> as a by\u2010product, which could only be detected on the basis of NMR analysis. Optimization of the purification and detection procedures allowed us to reach 96% purity required for biological assays of compound <jats:bold>5<\/jats:bold>. The same synthetic strategy was applied, using the \u0394<jats:sup>4<\/jats:sup>\u20103\u2010keto enone, 3\u2010oxoandrost\u20104\u2010en\u201017<jats:italic>\u03b2<\/jats:italic>\u2010yl acetate (<jats:bold>8<\/jats:bold>), as starting material, to prepare the potent aromatase inhibitor \u0394<jats:sup>4<\/jats:sup>\u2010olefin, androst\u20104\u2010en\u201017\u2010one (<jats:bold>15<\/jats:bold>). Unexpectedly, a different aromatase inhibitor, the \u0394<jats:sup>3,5<\/jats:sup>\u2010diene, androst\u20103,5\u2010dien\u201017\u2010one (<jats:bold>12<\/jats:bold>), was formed. To overcome this drawback, another strategy was developed for the preparation of <jats:bold>15<\/jats:bold> from <jats:bold>8<\/jats:bold>. The data now presented show the unequal reactivity of the two steroidal <jats:italic>A<\/jats:italic>\u2010ring \u0394<jats:sup>1<\/jats:sup>\u2010 and \u0394<jats:sup>4<\/jats:sup>\u20103\u2010hydroxy allylic alcohol intermediates, 3<jats:italic>\u03b2<\/jats:italic>\u2010hydroxy\u20105<jats:italic>\u03b1<\/jats:italic>\u2010androst\u20101\u2010en\u201017<jats:italic>\u03b2<\/jats:italic>\u2010yl acetate (<jats:bold>2<\/jats:bold>) and 3<jats:italic>\u03b2<\/jats:italic>\u2010hydroxyandrost\u20104\u2010en\u201017<jats:italic>\u03b2<\/jats:italic>\u2010yl acetate (<jats:bold>9<\/jats:bold>), towards SOCl<jats:sub>2<\/jats:sub>, and provides a new strategy for the preparation of the aromatase inhibitor <jats:bold>12<\/jats:bold>. Additionally, a new pathway to prepare compound <jats:bold>15<\/jats:bold> was achieved, which avoids the formation of undesirable by\u2010products.<\/jats:p>","DOI":"10.1002\/hlca.201300082","type":"journal-article","created":{"date-parts":[[2014,1,17]],"date-time":"2014-01-17T10:38:59Z","timestamp":1389955139000},"page":"39-46","source":"Crossref","is-referenced-by-count":3,"title":["Insights into the Synthesis of Steroidal <i>A<\/i>\u2010Ring Olefins"],"prefix":"10.1002","volume":"97","author":[{"given":"Carla L.","family":"Varela","sequence":"first","affiliation":[]},{"given":"Fernanda M. F.","family":"Roleira","sequence":"additional","affiliation":[]},{"given":"Saul C. P.","family":"Costa","sequence":"additional","affiliation":[]},{"given":"Alexandra S. C. T.","family":"Pinto","sequence":"additional","affiliation":[]},{"given":"Ana I. O. S.","family":"Martins","sequence":"additional","affiliation":[]},{"given":"Rui A.","family":"Carvalho","sequence":"additional","affiliation":[]},{"given":"Nat\u00e9rcia A.","family":"Teixeira","sequence":"additional","affiliation":[]},{"given":"Georgina","family":"Correia\u2010da\u2010Silva","sequence":"additional","affiliation":[]},{"given":"Elisi\u00e1rio","family":"Tavares\u2010da\u2010Silva","sequence":"additional","affiliation":[]}],"member":"311","published-online":{"date-parts":[[2014,1,17]]},"reference":[{"key":"e_1_2_1_1_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.steroids.2008.07.001"},{"key":"e_1_2_1_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0006-291X(89)80102-0"},{"key":"e_1_2_1_3_2","doi-asserted-by":"publisher","DOI":"10.1200\/JCO.2005.09.121"},{"key":"e_1_2_1_4_2","doi-asserted-by":"publisher","DOI":"10.1634\/theoncologist.11-10-1058"},{"key":"e_1_2_1_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.steroids.2006.10.009"},{"key":"e_1_2_1_6_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm050129p"},{"key":"e_1_2_1_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm300262w"},{"key":"e_1_2_1_8_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00338a016"},{"key":"e_1_2_1_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/jm00040a012"},{"key":"e_1_2_1_10_2","doi-asserted-by":"publisher","DOI":"10.1016\/0039-128X(75)90021-5"},{"key":"e_1_2_1_11_2","doi-asserted-by":"publisher","DOI":"10.1248\/cpb.13.1435"},{"key":"e_1_2_1_12_2","first-page":"1616","author":"Boynton J. 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