17480-08-9Relevant articles and documents
One-Pot Synthesis of Primary and Secondary Aliphatic Amines via Mild and Selective sp3 C?H Imination
Comito, Robert J.,Ghosh, Subrata K.,Hu, Mengnan
supporting information, p. 17601 - 17608 (2021/11/03)
The direct replacement of sp3 C?H bonds with simple amine units (?NH2) remains synthetically challenging, although primary aliphatic amines are ubiquitous in medicinal chemistry and natural product synthesis. We report a mild and selective protocol for preparing primary and secondary aliphatic amines in a single pot, based on intermolecular sp3 C?H imination. The first C?H imination of diverse alkanes, this method shows useful site-selectivity within substrates bearing multiple sp3 C?H bonds. Furthermore, this reaction tolerates polar functional groups relevant for complex molecule synthesis, highlighted in the synthesis of amine pharmaceuticals and amination of natural products. We characterize a unique C?H imination mechanism based on radical rebound to an iminyl radical, supported by kinetic isotope effects, stereoablation, resubmission, and computational modeling. This work constitutes a selective method for complex amine synthesis and a new mechanistic platform for C?H amination.
Sulfinates from Amines: A Radical Approach to Alkyl Sulfonyl Derivatives via Donor-Acceptor Activation of Pyridinium Salts
Andrews, Jonathan A.,Pantaine, Lo?c R. E.,Palmer, Christopher F.,Poole, Darren L.,Willis, Michael C.
, p. 8488 - 8493 (2021/11/01)
Synthetically versatile alkyl sulfinates can be prepared from readily available amines, using Katritzky pyridinium salt intermediates. In a catalyst-free procedure, primary, secondary, and benzylic alkyl radicals are generated by photoinduced or thermally induced single-electron transfer (SET) from an electron donor-acceptor (EDA) complex, and trapped by SO2 to generate sulfonyl radicals. Hydrogen atom transfer (HAT) from Hantzsch ester gives alkyl sulfinate products, which are used to prepare a selection of medicinal chemistry relevant sulfonyl-containing motifs.
Catalytic Reduction of Nitriles by Polymethylhydrosiloxane Using a Phenalenyl-Based Iron(III) Complex
Das, Shyamal,Das, Hari Sankar,Singh, Bhagat,Haridasan, Rahul Koottanil,Das, Arpan,Mandal, Swadhin K.
supporting information, p. 11274 - 11278 (2019/09/10)
The reduction of nitriles to primary amines using an inexpensive silane such as polymethylhydrosiloxane (PMHS) is an industrially important reaction. Herein we report the synthesis of an earth-abundant Fe(III) complex bearing a phenalenyl-based ligand that was characterized by mass spectroscopy, elemental analysis, cyclic voltammetry, and single-crystal X-ray diffraction. The complex showed excellent catalytic activity toward reduction of aromatic, heteroaromatic, aliphatic, and sterically crowded nitriles to produce primary amines using polymethylhydrosiloxane (PMHS).
