18670-81-0Relevant articles and documents
Bench-Stable Cobalt Pre-Catalysts for Mild Hydrosilative Reduction of Tertiary Amides to Amines and Beyond
Nurseiit, Alibek,Janabel, Jaysan,Gudun, Kristina A.,Kassymbek, Aishabibi,Segizbayev, Medet,Seilkhanov, Tulegen M.,Khalimon, Andrey Y.
, p. 790 - 798 (2019)
The readily synthesized and bench-stable cobalt dichloride complex (dpephos)CoCl2 is employed as a pre-catalyst for a diversity of silane additions to unsaturated organic molecules, including the normally challenging reduction of amides to amines. With regard to hydrosilative reduction of amides even more effective and activator free catalytic systems can be generated from the bench-stable, commercially available Co(acac)2 and Co(OAc)2 with dpephos and PPh3 ligands. These systems operate under mild conditions (100 °C), with many examples of room temperature transformations, presenting a first example of mild cobalt-catalyzed hydrosilylation of amides.
Erratum: Redox-Noninnocent Ligand-Supported Vanadium Catalysts for the Chemoselective Reduction of C=X (X = O, N) Functionalities (Journal of the American Chemical Society (2019) 141:38 (15230-15239) DOI: 10.1021/jacs.9b07062)
Zhang, Guoqi,Wu, Jing,Zheng, Shengping,Neary, Michelle C.,Mao, Jincheng,Flores, Marco,Trovitch, Ryan J.,Dub, Pavel A.
supporting information, p. 16507 - 16509 (2020/10/14)
Pages 15232, 15233, and 15236. In the original paper, the doublet wave functions for 21 and 21a/21b were incorrectly (Figure Presented). reported as spin-contaminated in sections 2.3 and 2.8 (Figure 3 and Scheme 9, respectively.) This comes from the incorrectly reported expected eigenvalue of 0.75 for the spin-squared operator ??2? for the antiferromagnetically coupled doublet |↓?L|↑↑?V state (originally given in the Supporting Information). The correct expected eigenvalue for the |↓?L|↑↑?V state should be 1.75. The wave functions for 21 and 21a/21b (eigenvalues 1.79 and 1.77/1.66, respectively) are therefore not spincontaminated. The corrected Figure 3 and Scheme 9 are presented below. A corrected Supporting Information file is also provided. The corrections do not affect any of the conclusions of the Article, but slightly decrease the gap between the quartet and doublet spin surfaces. Scheme 3 has been also corrected to reflect the fact that (CH3)3SiCH2 ? radicals can only react based on spin conservation.
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.
