49543-88-6Relevant articles and documents
Seeking Heteroatom-Rich Compounds: Synthetic and Mechanistic Studies into Iron Catalyzed Dehydrocoupling of Silanes
Coles, Nathan T.,Gasperini, Danila,King, Andrew K.,Mahon, Mary F.,Webster, Ruth L.
, p. 6102 - 6112 (2020/07/21)
A detailed synthetic investigation into the dehydrocoupling of silanes with amines, phosphines, and alcohols using an iron precatalyst (1) is presented. We have furnished over 30 examples of aminosilane synthesis along with kinetic studies using MeBnNH and MePhSiH2 as coupling partners. The kinetic studies suggest a reversible reaction with silane which generates aminosilane and an Fe-hydride dimer that undergoes rate-limiting protonolysis with amine with N-H bond cleavage in the transition state, consistent with a primary KIE of 2.42(3). The presence of dimers as on-cycle intermediates was analyzed in depth. Beyond this we have explored the substrate scope of phosphinosilane formation which shows a preferential heterodehydrocoupling to give the phosphinosilane with primary and secondary silanes. Silylethers can also be prepared and alcohols that contain alkene functionality do not show any tendency to reduce the double bond.
Preparation Of Aromatic-Substituted Silylamines By The Dehydrogenative Coupling Of Aromatic-Substituted Amine N-H And Si-H Bonds
-
Paragraph 0030; 0032; 0168-0170, (2019/07/29)
The present disclosure is directed at methods of forming an N—Si silyl bond, the method comprising contacting an organic substrate comprising an aromatic amine having at least one N—H bond with a mixture comprising of (a) at least one hydrosilane or hydrosiloxane and (b) at least one hydroxide or alkoxide, under conditions sufficient to form the N—Si bond. The disclosure is further directed to the compositions involved in these methods and the products that result therefrom.
Iridium-catalyzed regioselective silylation of aromatic and benzylic C-H bonds directed by a secondary amine
Li, Qian,Driess, Matthias,Hartwig, John F.
supporting information, p. 8471 - 8474 (2014/08/18)
Reported herein is an iridium-catalyzed, regioselective silylation of the aromatic C-H bonds of benzylamines and the benzylic C-H bonds of 2,N-dialkylanilines. In this process, (hydrido)silyl amines, generated in situ by dehydrogenative coupling of benzylamine or aniline with diethylsilane, undergo selective silylation at the C-H bond γ to the amino group. The products of this silylation are suitable for subsequent oxidation, halogenation, and cross-coupling reactions to deliver benzylamine and arylamine derivatives.
