117635-35-5Relevant academic research and scientific papers
Boosting Conjugate Addition to Nitroolefins Using Lithium Tetraorganozincates: Synthetic Strategies and Structural Insights
Dell'Aera, Marzia,Perna, Filippo Maria,Vitale, Paola,Altomare, Angela,Palmieri, Alessandro,Maddock, Lewis C. H.,Bole, Leonie J.,Kennedy, Alan R.,Hevia, Eva,Capriati, Vito
supporting information, p. 8742 - 8748 (2020/07/04)
We report the first transition metal catalyst- and ligand-free conjugate addition of lithium tetraorganozincates (R4ZnLi2) to nitroolefins. Displaying enhanced nucleophilicity combined with unique chemoselectivity and functional group tolerance, homoleptic aliphatic and aromatic R4ZnLi2 provide access to valuable nitroalkanes in up to 98 % yield under mild conditions (0 °C) and short reaction time (30 min). This is particularly remarkable when employing β-nitroacrylates and β-nitroenones, where despite the presence of other electrophilic groups, selective 1,4 addition to the C=C is preferred. Structural and spectroscopic studies confirmed the formation of tetraorganozincate species in solution, the nature of which has been a long debated issue, and allowed to unveil the key role played by donor additives on the aggregation and structure of these reagents. Thus, while chelating N,N,N’,N’-tetramethylethylenediamine (TMEDA) and (R,R)-N,N,N’,N’-tetramethyl-1,2-diaminocyclohexane (TMCDA) favour the formation of contacted-ion pair zincates, macrocyclic Lewis donor 12-crown-4 triggers an immediate disproportionation process of Et4ZnLi2 into equimolar amounts of solvent-separated Et3ZnLi and EtLi.
Deoxycholic acid-derived biaryl phosphites as versatile and enantioselective ligands in the rhodium-catalyzed conjugate addition of arylboronic acids to nitroalkenes
Jumde, Varsha R.,Iuliano, Anna
supporting information, p. 3475 - 3483 (2013/12/04)
A highly enantioselective conjugate addition of arylboronic acids to cyclic as well as acyclic aromatic and aliphatic nitroalkenes is presented. The rhodium complexes obtained from deoxycholic acid-derived binaphthyl and flexible biphenyl phosphites showed good activity as well as very high enantioselectivity (ee up to 99%) in the conjugated addition even in the presence of challenging substrates such as 1-nitrocyclohexene or aliphatic acyclic nitroalkenes. Copyright
Synthesis of 1,1-Diaryl-2,2-dimethoxyethanes
Ashwood, Michael S.,Bell, Lawrence A.,Houghton, Peter G.,Wright, Stanley H. B.
, p. 379 - 381 (2007/10/02)
The 1,4-addition of Grignard reagents to β-nitrostyrene to give 1,1-diaryl-2-nitroethanes and their subsequent conversion via a modified Nef reaction into 1,1-diaryl-2,2-dimethoxyethanes (diarylacetaldehyde dimethyl acetals) is described.The scope of the reaction has been briefly explored and one example demonstrated on a large scale.
