85633-79-0Relevant academic research and scientific papers
The Influence of Acetoxy Substituents on the Nucleophilicity of Alkyl Radicals
Giese, Bernd,Engelbrecht, Renate,Erfort, Ulrich
, p. 1289 - 1293 (2007/10/02)
Reduction of the organomercuric salt 3 with NaBH4 yields the acetoxy-substituted radical 4.Using competition techniques the rel. rates of addition of 4 to alkenes 5 can be measured.The rate data show that radical 4 is a nucleophile (table 1) but the nucleophilicity is slightly smaller than that of the sec. cyclohexyl radical (figure 1).The acetoxy group, therefore, acts as an electron withdrawing substituent that reduces the nucleophilic reactivity and the nucleophilic selectivity of alkyl radicals.
Reactions with Umpolung via Radicals: CC-Bond Formation between Ketones and Alkenes
Giese, Bernd,Erfort, Ulrich
, p. 1240 - 1251 (2007/10/02)
The hydrazones 1 - 11 from ketones react in a general synthetic procedure with alkenes 33a - m to yield products 34 - 44 (table 2 and 3).Important intermediates of these reactions with umpolung are 1-acetoxyalkyl radicals 49 that are formed from organomercuric salts 14 - 24 by reduction with NaBH4.This new CC-bond formation reaction can be carried out in a one-pot synthesis without isolation of the metalorganic compounds (table 4). - In side reactions the reduction products 50 are formed, if bulky starting compounds or less reactive alkenes are used (table 5 and 6).
