Mn-, Fe-, and Co-Catalyzed Radical Hydrofunctionalizations of Olefins

Abstract

Cofactor-mimetic aerobic oxidation has conceptually merged with catalysis of syngas reactions to form a wide range of Markovnikov-selective olefin radical hydrofunctionalizations. We cover the development of the field and review contributions to reaction invention, mechanism and application to complex molecule synthesis. We also provide a mechanistic framework for understanding this compendium of radical reactions.

Stereoselective and Regioselective Synthesis of Heterocycles via Copper-Catalyzed Additions of Amine Derivatives and Alcohols to Alkenes

“…Cobalt(III), 23–26 iron(III), 27 and copper(II) (vide infra) have all demonstrated this propensity. 28 A stoichiometric oxidant to turn over the catalyst is required to perform these net oxidative reactions.…”

Divergent Total Syntheses of Enmein‐Type Natural Products: (−)‐Enmein, (−)‐Isodocarpin, and (−)‐Sculponin R

“…Notably,attempts with other allylic oxidation methods were unfruitful for this transformation. Subsequent Mukaiyama hydration [17] followed by deacetylation using Me 3 SnNMe 2 , [18] completed the total synthesis of sculponin R, which is spectroscopically identical to the natural sample reported by Sun and co-workers. [16] Allylic oxidation by selenium dioxide followed by treatment with Dess-Martin periodinane gave enone 21.…”

Navigating the Chiral Pool in the Total Synthesis of Complex Terpene Natural Products

“…It is notable that the chirality of the pinene nucleus subtlety orchestrates all aspects of selectivity in this tandem process, which also serves to further showcase the power of metal-catalyzed, radical-based hydrofunctionalization chemistry in the rapid assembly of molecular complexity. 70 Moreover, this work highlights the power of biosynthetic planning in the efficient chemical synthesis of terpenes. 71 …”