A decarboxylative borylation of aliphatic acids for the synthesis of a variety of alkylboronates has been developed by mixing m-chloroperoxybenzoic acid (mCPBA)activated fatty acids with bis(catecholato)diboron in N,Ndimethylformamide (DMF) at room temperature. A radical chain process is involved in the reaction which initiates from the B−B bond homolysis followed by the radical transfer from the boron atom to the carbon atom with subsequent decarboxylation and borylation.

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An ovel radical 1,4/5-amino shift from the oxygen center of alkene-tethered diphenyl ketoxime ethers to the carbon center to achieve high value-added fluoroalkyl-containing primary b(g)-amino-ketones is reported. Mechanism studies reveal that the migration is triggered by the alkene addition of fluoroalkyl radical derived from the electron donor-acceptor (EDA) complex of Tognisr eagent II or fluoroalkyl iodides and quinuclidine,a nd involves au nique 5(6)-exo-trig cyclization of the carbon-centered radical onto the N-atom of ketoxime ethers followed by acascade sequence of NÀObond cleavage and dehydrogenation. Notably,besides Tognisreagent II and fluoroalkyl iodides,this protocol is also compatible with other radical precursors to provide various functionalizedprimary aminoketones.

This paper reports two new visible-light-promoted radical reactions of α-azido amides. By catalysis of [Ir­(ppy)2(dtbbpy)]­PF6 with i-Pr2NEt as the reducing agent, N-aryl α-azido tertiary amides were first converted to the corresponding aminyl radicals through reduction of the azido group; the aminyl radicals then underwent N-to-N aryl migration to give α-anilinyl-functionalized amides. α-Azido secondary amides, on the other hand, reacted with the solvent ethanol and i-Pr2NEt to afford the imidazolinone products.

An ovel radical 1,4/5-amino shift from the oxygen center of alkene-tethered diphenyl ketoxime ethers to the carbon center to achieve high value-added fluoroalkyl-containing primary b(g)-amino-ketones is reported. Mechanism studies reveal that the migration is triggered by the alkene addition of fluoroalkyl radical derived from the electron donor-acceptor (EDA) complex of Tognisr eagent II or fluoroalkyl iodides and quinuclidine,a nd involves au nique 5(6)-exo-trig cyclization of the carbon-centered radical onto the N-atom of ketoxime ethers followed by acascade sequence of NÀObond cleavage and dehydrogenation. Notably,besides Tognisreagent II and fluoroalkyl iodides,this protocol is also compatible with other radical precursors to provide various functionalizedprimary aminoketones.

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A novel radical decarboxylative 1,2,3-trifunctionalization of various 3-enoic acids is achieved via 1,4-imino-N shift by using CF3I as trifluoromethylating reagent and the readily available aryl ketoximes as both acid activator and difunctionalization reagent. This reaction is performed by CF3-radical addition on the terminal alkene moiety of in-situ formed aryl ketoxime 3-enoates, followed by a cascade radical 1,4-imino-N shift/decarboxylation/arylation to furnish the N-atom at 2-position of alkenes and to fix the aryl group at 3-position by replacing the carboxyl group. Consequently, a series of 1,2,3-trifunctionalized allyl derivatives are efficient produced in the form of structurally important trifluoromethylated 3,4-dihydroisoquinolines (3,4-DHIQs). Other functional radicals such as diverse fluoroalkyl and azido radicals can also trigger the reaction. This tactic not only provides a new conversion mode for 3-enoic acids and aryl ketoximes, but also affords unprecedent modular method for constructing diverse functionalized 3,4-polysubstituted DHIQs with excellent regio- and diastereoselectivity and bioactive molecules compatibility.