Copper‐Catalyzed Oxy‐Alkenylation of Homoallylic Alcohols to Generate Functional syn‐1,3‐Diol Derivatives

Abstract

A novel method for the synthesis of a wide range of functionalized 1,3-diol derivatives is reported. Employing a copper-catalyzed oxy-alkenylation strategy, a range of readily available, substituted homoallylic alcohol derivatives and alkenyl(aryl) iodonium salts combine to form syn-1,3-carbonates in excellent yield and with high selectivity. Furthermore, the products formed are amenable to an iterative reaction sequence, thus affording highly complex polyketide-like fragments.

Synthesis of 1,3-Diols by O-Nucleophile Additions to Activated Alkenes

“…An amazing copper-catalyzed oxy-alkenylation was described by Gaunt and Holt. 58 The combination of copper salts with aryl(alkenyl)iodonium reagents provides highly electrophilic species that can react with double bonds thus activating the addition of oxygen nucleophiles. The reaction is performed with carbamates and under hydrolytic conditions the 1,3-diols are obtained as carbonates.…”

Novartis Chemistry Lectureship 2015–2016

“…Gaunt was on the Academic Advisory Board of Advanced Synthesis & Catalysis from 2011–2015. He has recently reported in Angewandte Chemie on copper‐catalyzed oxy‐alkenylation reactions …”

Novartis Chemistry Lectureship 2015–2016

“…Gaunt gehörte 2011–2015 dem Academic Advisory Board von Advanced Synthesis & Catalysis an. Kürzlich hat er in der Angewandten Chemie kupferkatalysierte Oxy‐Alkenylierungen vorgestellt …”