{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,10,9]],"date-time":"2025-10-09T01:08:27Z","timestamp":1759972107365,"version":"build-2065373602"},"reference-count":54,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2015,1,21]],"date-time":"2015-01-21T00:00:00Z","timestamp":1421798400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Chemistry \u0097 An Asian Journal"],"published-print":{"date-parts":[[2015,4]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Novel conditions for the transformation of <jats:italic>gem<\/jats:italic>\u2010dibromomethylenes to ketones are described. <jats:italic>gem<\/jats:italic>\u2010Dibromo compounds were treated with acetic anhydride and triethylamine in dichloromethane\/water at room temperature under an air atmosphere to give the corresponding ketones in moderate yields. A radical mechanism is proposed based on experimental results.<\/jats:p>","DOI":"10.1002\/asia.201403277","type":"journal-article","created":{"date-parts":[[2015,1,21]],"date-time":"2015-01-21T08:00:08Z","timestamp":1421827208000},"page":"1035-1041","source":"Crossref","is-referenced-by-count":3,"title":["Unexpected Metal\u2010Free Transformation of <i>gem<\/i>\u2010Dibromomethylenes to Ketones under Acetylation Conditions"],"prefix":"10.1002","volume":"10","author":[{"given":"Rino","family":"Kimura","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Yusuke","family":"Sawayama","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Atsuo","family":"Nakazaki","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Kazunori","family":"Miyamoto","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Masanobu","family":"Uchiyama","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Toshio","family":"Nishikawa","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2015,1,21]]},"reference":[{"key":"e_1_2_6_1_2","doi-asserted-by":"publisher","DOI":"10.5059\/yukigoseikyokaishi.70.1178"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201102494"},{"key":"e_1_2_6_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201102494"},{"key":"e_1_2_6_3_2","first-page":"651","author":"Sawayama Y.","year":"2011","journal-title":"Synlett"},{"key":"e_1_2_6_4_2","unstructured":"For preparation of compound7 see the Supporting Information."},{"key":"e_1_2_6_5_2","unstructured":"The structure of9was deduced by analysis of the NMR IR and MS spectra. A possible mechanism for the formation of9may be the competitive degradation of a peroxide intermediate (see the Supporting Information) similar to that ofEin Scheme\u20056 although no experimental evidence has been obtained."},{"key":"e_1_2_6_6_2","unstructured":"Under the conditions of entry\u20057 ketone8was obtained in 37\u2009% yield along with an acetylated product in 28\u2009% yield which was quantitatively hydrolyzed with silica gel to8. The reported 65\u2009% yield is the combined yield after hydrolysis."},{"key":"e_1_2_6_7_2","unstructured":"The reaction of4under the conditions of entry\u20057 in Table\u20051 provided enol acetate5contaminated with inseparable and unidentified by\u2010products."},{"key":"e_1_2_6_8_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0040-4020(96)00981-7"},{"key":"e_1_2_6_9_2","unstructured":"In terms of yield the conditions of entry\u20057 proved to be better than those of entry\u20052."},{"key":"e_1_2_6_10_2","unstructured":"The reaction was performed using 1.00\u2005mmol of substrate under the conditions of entry\u20057 in Table\u20051 with slight modifications. For details see the Experimental Section."},{"key":"e_1_2_6_11_2","unstructured":"The reduction of terminal dibromomethylene and dibromocyclopropyl groups with Bu3SnH without radical initiators has been reported:"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00841a037"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00827a053"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01038a025"},{"key":"e_1_2_6_15_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00129a028"},{"key":"e_1_2_6_16_2","unstructured":"When compound8was stirred vigorously with CH2Cl2\u2010H218O for 20\u2005min at rt ESI\u2010MS analysis of the organic layer indicated the incorporation of18O into compound8."},{"key":"e_1_2_6_17_2","unstructured":"These18O\u2010labelling experiments were carried out with reference to the following papers and the experimental details provided by Prof. Y. Hayashi (Tohoku Univ.);"},{"key":"e_1_2_6_18_2","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1113553108"},{"key":"e_1_2_6_19_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201403475"},{"key":"e_1_2_6_20_2","unstructured":"\u00a0"},{"key":"e_1_2_6_21_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00209a049"},{"key":"e_1_2_6_22_2","doi-asserted-by":"publisher","DOI":"10.1071\/CH9830719"},{"key":"e_1_2_6_23_2","unstructured":"PET (photoinduced electron transfer) may be a possible alternative mechanism for generation of radicalC. However the reactions of thegem\u2010dibromides in this study did not require UV or visible light. For several examples of PET in organic synthesis see:"},{"key":"e_1_2_6_24_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1989-27214"},{"key":"e_1_2_6_25_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(94)88271-1"},{"key":"e_1_2_6_26_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4020(95)00727-P"},{"key":"e_1_2_6_27_2","doi-asserted-by":"publisher","DOI":"10.1016\/0040-4039(96)01032-5"},{"key":"e_1_2_6_28_2","first-page":"397","author":"Sha C.\u2010K.","year":"1998","journal-title":"Chem. Commun."},{"key":"e_1_2_6_29_2","unstructured":"Another possible mechanism for the initiation may involve oxygen. For examples see:"},{"key":"e_1_2_6_30_2","doi-asserted-by":"publisher","DOI":"10.1055\/s-1997-5779"},{"key":"e_1_2_6_31_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00023a076"},{"key":"e_1_2_6_32_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja4052685"},{"key":"e_1_2_6_33_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja00353a039"},{"key":"e_1_2_6_34_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00031a055"},{"key":"e_1_2_6_35_2","unstructured":"The reaction of7was conducted with Ac2O\u2010d6instead of Ac2O to give CD3CONEt2 as observed by1H\u2005NMR spectroscopy."},{"key":"e_1_2_6_36_2","unstructured":"Most of the substrates reported possessesgem\u2010CBr2group at easily hydrolyzable benzylic positions. For the several examples see:"},{"key":"e_1_2_6_37_2","doi-asserted-by":"publisher","DOI":"10.1002\/jhet.5570450338"},{"key":"e_1_2_6_38_2","doi-asserted-by":"publisher","DOI":"10.1080\/00397910801916223"},{"key":"e_1_2_6_39_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.tet.2008.02.064"},{"key":"e_1_2_6_40_2","unstructured":"For recent reviews of metal\u2010free transformations see:"},{"key":"e_1_2_6_41_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2031"},{"key":"e_1_2_6_42_2","doi-asserted-by":"publisher","DOI":"10.1039\/c3ra40813b"},{"key":"e_1_2_6_43_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2012.130"},{"key":"e_1_2_6_44_2","doi-asserted-by":"publisher","DOI":"10.1021\/ol5018883"},{"key":"e_1_2_6_45_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201206518"},{"key":"e_1_2_6_45_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201206518"},{"key":"e_1_2_6_46_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja103050x"},{"key":"e_1_2_6_47_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja2092163"},{"key":"e_1_2_6_48_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ejmech.2009.01.028"},{"key":"e_1_2_6_49_2","unstructured":"\u00a0"},{"key":"e_1_2_6_50_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo00389a004"},{"key":"e_1_2_6_51_2","doi-asserted-by":"publisher","DOI":"10.1021\/jo01050a004"},{"key":"e_1_2_6_52_2","doi-asserted-by":"publisher","DOI":"10.1246\/cl.2012.658"}],"container-title":["Chemistry \u2013 An Asian Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/api.wiley.com\/onlinelibrary\/tdm\/v1\/articles\/10.1002%2Fasia.201403277","content-type":"unspecified","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/asia.201403277","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,8]],"date-time":"2025-10-08T19:17:27Z","timestamp":1759951047000},"score":1,"resource":{"primary":{"URL":"https:\/\/aces.onlinelibrary.wiley.com\/doi\/10.1002\/asia.201403277"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,1,21]]},"references-count":54,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2015,4]]}},"alternative-id":["10.1002\/asia.201403277"],"URL":"https:\/\/doi.org\/10.1002\/asia.201403277","archive":["Portico"],"relation":{},"ISSN":["1861-4728","1861-471X"],"issn-type":[{"type":"print","value":"1861-4728"},{"type":"electronic","value":"1861-471X"}],"subject":[],"published":{"date-parts":[[2015,1,21]]}}}