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TheCo2(CO)8-mediated intramolecular Pauson–Khandreaction is an efficient approach to the trans-decalinsubunit with a defined C1 quaternary chiral center. The newly developeddensity functional theory method M11-L was employed to study the mechanism,reactivity, and stereoselectivity for this reaction. The rate- andstereoselectivity-determining step is the intramolecular alkene insertioninto the carbon–cobalt bond. Insertion of the alkene by the re- and si-face was studied to explainthe stereoselectivity. The effects of varying the substituent on theacetylene and the C3 chirality were investigated experimentally andtheoretically. [ABSTRACT FROM AUTHOR]

A transition-metal-assistedoxidative C(sp3)-H/N–Hcross-coupling reaction of N-alkoxyamides with aliphatichydrocarbons is described. During the reaction, nitrogen radicalswere generated from the oxidation of N-alkoxyamides.Experiments and DFT calculations revealed that transition-metal catalystcould lower the reactivity of the generated nitrogen radical by thecoordination of the transition metal, which allowed the selectiveradical/radical cross-coupling with the transient sp3carbonradical to construct C(sp3)–-N bonds. Various C(sp3)–H bonds could be transformed into C(sp3)–N bonds through this radical amidation strategy. [ABSTRACT FROM AUTHOR]