Iron‐Catalyzed C(sp³)C(sp³) Bond Formation through C(sp³)H Functionalization: A Cross‐Coupling Reaction of Alcohols with Alkenes

Molecular iodine as a mild catalyst for cross-coupling of alkenes and alcohols

“…The majority of known methods include the use of very effective transition metal catalysts, such as complexes of Pd, Cu, Ni, Fe, Ru and Lewis acids based on weak metals (e.g. Bi, In and Ga) [7][8][9][10][11][12][13][14][15][16][17]. However, toxicity of organometallic reagents and their removal to meet the strict specifications of pharmaceutical grade purity is a challenging and demanding process.…”

Four Pathways in Radical Alkylation of Isocyanide with Simple Alcohol

“…Finally, the computed Gibbs free energy profile for the four pathways in reaction of 1-pentanol (1) with 2isocyano-5-methyl-1,1'-biphenyl (2) have been carried out (Figures 4-6, see also the SI). It can be seen from Figure 4 that the rate-determining step (RDS) in path I and path II is HAT from alcohol to radical A (the barrier is 19.1 kcal/mol, which is consistent with the KIE result.)…”

“…[1] There are usually four pathways in these transformations (Scheme 1). Path I is the hydroxyalkylation via a Ccentered radical intermediate by direct hydrogen-atom-transfer (HAT) of the α-hydroxyl CÀ H, which has been well-developed by Tu, [2] Han and Pan, [3] and Liu [4] et al [5] A dehydroxylative alkylation via spin-centershift (SCS) [6] from the same intermediate represents the second process, which is widely found in biological system. Besides, an alkoxyl radical intermediate could be often formed via one-electron oxidation followed by deprotonation of alcohol.…”

“…Initially we evaluated the substrate scope after modification of the reaction conditions ( Table 1 and 2). As illustrated in Table 1, a series of 6-ethylphenanthridines can be smoothly synthesized in moderate to good yield (1)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12).…”

Iron Catalysis in Synthetic Chemistry

“…With the use of the relatively high activity of the α-C-H bond of a heteroatom, Tu and co-workers (102) reported this type of radical quenching using terminal alkenes (Scheme 83). Controlled experiments, deuterium labeling, and cross-over experiments were conducted to give an idea about the possible mechanism.…”