Mild Aerobic Oxidation of Secondary Alcohols with Water Tolerant Cu(I) Catalyst.

Green, aerobic oxidation of secondary alcohols to ketones poses a significant synthetic challenge. To address this, we have developed a highly active (DPA)CuI/ABNO catalyst system capable of aerobically oxidizing a wide range of secondary alcohols, including benzylic and aliphatic derivatives, yielding the corresponding ketones with high yields. The unique feature of this Cu(I) catalyst is its high stability, even in the presence of water.

Intramolecular substitutions of secondary and tertiary alcohols with chirality transfer by an iron(III) catalyst.

Optically pure alcohols are abundant in nature and attractive as feedstock for organic synthesis but challenging for further transformation using atom efficient and sustainable methodologies, particularly when there is a desire to conserve the chirality. Usually, substitution of the OH group of stereogenic alcohols with conservation of chirality requires derivatization as part of a complex, stoichiometric procedure. We herein demonstrate that a simple, inexpensive, and environmentally benign iron(III) catalyst promotes the direct intramolecular substitution of enantiomerically enriched secondary and tertiary alcohols with O-, N-, and S-centered nucleophiles to generate valuable 5-membered, 6-membered and aryl-fused 6-membered heterocyclic compounds with chirality transfer and water as the only byproduct.