Metal-hydride hydrogen atom transfer (MHAT) functionalizes alkenes with predictable branched (Markovnikov) selectivity. The breadth of these transformations has been confined to π-radical traps; no sp3 electrophiles have been reported. Here we describe a Mn/Ni dual catalytic system that hydroalkylates unactivated olefins with unactivated alkyl halides, yielding aliphatic quaternary carbons.

A novel strategy for the synthesis of δ-thiolactones from inexpensive and readily available γ-unsaturated esters has been developed. This strategy incorporates a radical acyl thiol–ene reaction as the key C–S bond forming step. Cyclization is achieved via a Steglich-type thiolactonization of 5-mercaptopentanoic acids. We report the facile and scalable synthesis of δ-thiolactones in moderate to good yield under mild reaction conditions with tolerance for a range of functional groups.

A new synthetic approach to thiolactones that employs an efficient acyl thiol-ene (ATE) or acyl thiol-yne (ATY) cyclization to convert unsaturated thiocarboxylic acid derivatives into thiolactones under very mild conditions is described. The high overall yields, fast kinetics, high diastereoselectivity, excellent regiocontrol, and broad substrate scope of these reaction processes render this a very useful approach for diversity-oriented synthesis and drug discovery efforts. A detailed computational rationale is provided for the observed regiocontrol.

A mild, inexpensive and general photocatalytic initiation protocol for anti-Markovnikov hydrothiolation of olefins using carbon nanomaterial/metal oxide (Carbon NM-MO) composites is reported. Graphene oxide (GO), nanodiamonds (ND) and carbon nano-onions (CNO) displaying bismuth or tungsten oxide nanoparticles adhered to the surface, function as highly efficient photocatalysts for thiol-ene ligation under both UV and visible-light-mediated The Supporting Information is available free of charge on the ACS Publications website at DOI:xxxxx Experimental procedures for nanocomposites preparation, Bright-field TEM of Bi 2 O 3-ox-CNO/GO nanocomposites, XPS of Bi 2 O 3 , 1 Hand 13 C-NMR Spectra of thioether and thioester products.

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