2739-12-0Relevant articles and documents
N-Methylaniline-induced Si-Si bond cleavages of perchlorooligosilanes
Park, Sung Jin,Choi, Jong Min,Cho, Hyeon Mo,Kim, Cheol Hyun,Lee, Myong Euy
, p. 140 - 144 (2014)
This study describes Si-Si bond cleavage of perchlorooligosilane using an amine. N-Methylaniline-induced Si-Si bond cleavage reactions of cyclic perchlorosilanes Si5Cl10 (1) and Si4Cl 8 (2), and acyclic perchlor
Formal Aniline Synthesis from Phenols through Deoxygenative N-Centered Radical Substitution
Lardy, Samuel W.,Luong, Kristine C.,Schmidt, Valerie A.
supporting information, p. 15267 - 15271 (2019/12/11)
Phenolic, lignin-derived substrates have emerged as desirable biorenewable chemical feedstocks for coupling reactions. A radical-mediated conversion of phenol derivatives to anilines is reported, using unfunctionalized hydroxamic acids as the N-centered radical source. The applicability of this triethyl phosphite mediated O-atom transfer approach, which tolerates a range of steric and electronic demands to naturally occurring phenols and lignin models, has been demonstrated in this work to access the corresponding aniline derivatives.
Magnesium-catalyzed mild reduction of tertiary and secondary amides to amines
Lampland, Nicole L.,Hovey, Megan,Mukherjee, Debabrata,Sadow, Aaron D.
, p. 4219 - 4226 (2015/11/11)
The first example of a catalytic hydroboration of amides for their deoxygenation to amines is reported. This transformation employs an earth-abundant magnesium-based catalyst. Tertiary and secondary amides are reduced to amines at room temperature in the presence of pinacolborane (HBpin) and catalytic amounts of ToMMgMe (ToM = tris(4,4-dimethyl-2-oxazolinyl)phenylborate). Catalyst initiation and speciation is complex in this system, as revealed by the effects of concentration and order of addition of the substrate and HBpin in the catalytic experiments. ToMMgH2Bpin, formed from ToMMgMe and HBpin, is ruled out as a possible catalytically relevant species by its reaction with N,N-dimethylbenzamide, which gives Me2NBpin and PhBpin through C-N and C-C bond cleavage pathways, respectively. In that reaction, the catalytic product benzyldimethylamine is formed in only low yield. Alternatively, the reaction of ToMMgMe and N,N-dimethylbenzamide slowly gives decomposition of ToMMgMe over 24 h, and this interaction is also ruled out as a catalytically relevant step. Together, these data suggest that catalytic activation of ToMMgMe requires both HBpin and amide, and ToMMgH2Bpin is not a catalytic intermediate. With information on catalyst activation in hand, tertiary amides are selectively reduced to amines in good yield when catalytic amounts of ToMMgMe are added to a mixture of amide and excess HBpin. In addition, secondary amides are reduced in the presence of 10 mol % ToMMgMe and 4 equiv of HBpin. Functional groups such as cyano, nitro, and azo remain intact under the mild reaction conditions. In addition, kinetic experiments and competition experiments indicate that B-H addition to amide C-O is fast, even faster than addition to ester C=O, and requires participation of the catalyst, whereas the turnover-limiting step of the catalyst is deoxygenation.
