{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,26]],"date-time":"2026-09-26T15:37:39Z","timestamp":1790437059604,"version":"4.1.0"},"reference-count":81,"publisher":"Wiley","issue":"31","license":[{"start":{"date-parts":[[2015,6,26]],"date-time":"2015-06-26T00:00:00Z","timestamp":1435276800000},"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":[[2015,7,27]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>The lithiation of halogenated azobenzenes by halogen\u2013lithium exchange commonly leads to substantial degradation of the azo group to give hydrazine derivatives besides the desired aryl lithium species. Yields of quenching reactions with electrophiles are therefore low. This work shows that a transmetalation reaction of easily accessible stannylated azobenzenes with methyllithium leads to a near\u2010quantitative lithiation of azobenzenes in <jats:italic>para<\/jats:italic>, <jats:italic>meta<\/jats:italic>, and <jats:italic>ortho<\/jats:italic> positions. To investigate the scope of the reaction, various lithiated azobenzenes were quenched with a variety of electrophiles. Furthermore, mechanistic <jats:sup>119<\/jats:sup>Sn NMR spectroscopic studies on the formation of lithiated azobenzenes are presented. A tin ate complex of the azobenzene was detected and characterized at low temperature.<\/jats:p>","DOI":"10.1002\/chem.201500003","type":"journal-article","created":{"date-parts":[[2015,6,26]],"date-time":"2015-06-26T22:43:56Z","timestamp":1435358636000},"page":"11165-11173","source":"Crossref","is-referenced-by-count":20,"title":["High\u2010Yield Lithiation of Azobenzenes by Tin\u2013Lithium Exchange"],"prefix":"10.1002","volume":"21","author":[{"given":"Jan","family":"Strueben","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Matthias","family":"Lipfert","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jan\u2010Ole","family":"Springer","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Colin A.","family":"Gould","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul J.","family":"Gates","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Frank D.","family":"S\u00f6nnichsen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Anne","family":"Staubitz","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2015,6,26]]},"reference":[{"key":"e_1_2_6_1_2","volume-title":"Industrial Dyes: Chemistry, Properties, Applications","author":"Hunger K. 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This would inevitably result in an uncontrolled and irreproducible warming of thenBuLi\/THF solution. In this context note that Table\u20051 merely represents the optimization process on a small scale."},{"key":"e_1_2_6_53_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.433131"},{"key":"e_1_2_6_54_2","unstructured":"For the experiments summarized in Table\u20051 the reactions were quenched after 4\u2005min but in the case of the NMR experiments they were not. The quenching reaction is an exothermic process and at the interface between the added droplet with the electrophile and the reaction mixture containing the nucleophile local heating will lead to the observed reaction products. Moreover diffusion at low temperatures is so slow that mixing of the reaction components becomes important. Whereas the reactions in Table\u20051 were all performed with stirring this was not possible in the NMR tube. Moreover the surface\/volume ratio of the NMR tube is much larger than of the reaction vessels used in the experiments in Table\u20051 so that the cooling efficiency will be much higher in the case of the NMR experiments. Therefore the reactions in the NMR tube were much slower than the stirred reactions described in Table\u20051."},{"key":"e_1_2_6_55_2","unstructured":"At this low temperature no temperature stability can be assumed. The temperature varied by 7\u2005K. 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