Am ethod for the cobalt-catalyzed alkylation-peroxidation of alkenes with 1,3-dicarbonyl compounds and Thydro (tert-butyl hydroperoxide solution) was developed. This approachp rovides practical and selective access to g-carbonyl peroxides in as ingles tep by startingf rom readily availables tarting materials. In addition, gram-scale syntheses demonstrated that the protocol is practical and useful for organic synthesis. Scheme1.Synthetic strategies for a-CÀHf unctionalization of carbonyl compounds (E = electrophile, M = metal,Ln= ligand, FG = functional group).Scheme2.Alkylation-peroxidation of alkenes.[a] S.GeneralP rocedure for Synthesis of 5:T oadry Schlenk tube were added 2-[2-(tert-butylperoxy)-2-phenylethyl]-1,3-diphenylpropane-1,3-dione (3a,0 .2 mmol), amine 4 (0.24 mmol), and anhydrous MeCN (1.0 mL) at room temperature. Then, TfOH (0.2 mmol) was added to the solution, and the resulting mixture was stirred at 85 8Cf or 1h.A fter cooling the mixture to room temperature, the solvent was evaporated under vacuum. The residue was purified by flash column chromatography on silica gel (ethyl acetate/ petroleum ether)t ogive product 5.

Transition metal-catalyzed allylic substitution reactions have evolved as versatile and powerful tools for organic synthesis. 1 Active allylic substrates bearing halides, acetates, carbonates, etc. as leaving groups are commonly used in allylic substitution reactions. The development of allylic substrates involving readily

Selective CÀOb ond cleavagei so fh igh interest for moderno rganic synthesis. As trategy for selective allylic CÀOb ond cleavage using ethyl salicylate as ad irecting leaving group has been developed. The reactioni si nitiated by the chelation of the ortho-ester phenolic group with iron catalyst. The p-allyl iron intermediate is generated and reacts with Grignardr eagents to give the allylic substitution products. The excellent selectivity of CÀO bond cleavage is achieved in multiple allylic CÀOb ondcontaining substrates with the aid of the salicylate-directed strategy.

Iron-catalyzed divergent tandem radical annulations of aldehydes with olefins are reported. The new strategy allows the rapid and efficient construction of various multifunctionlized indolines (R = Ar) and dihydropyrans (R = Me), which are significant skeletons in bioactive natural products and pharmaceuticals. The substituents of tertiary amines play vital roles to facilitate the desired transformation. Mechanistic studies on indoline formation disclose that the homolytic cleavage of the carbonyl C-H bond might be involved in the rate-determining step, while dissociation of the aromatic C-H bond was most likely included in the product-determining step.

The reaction proceeds via a radical pathway as is demonstrated by addition of an intermediately formed methyl radical (from tBu‐O‐O‐tBu) in absence of any aldehyde yielding compound (XVI) and the formation of indoline derivative (XVIII) when toluene is used as the solvent.