Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals

Abstract

<div> <div> <div> <p>A manganese-catalyzed electrochemical deconstructive chlorination of cycloalkanols has been developed. This electrochemical method provides access to alkoxy radicals from alcohols and exhibits a broad substrate scope, with various cyclopropanols and cyclobutanols converted into synthetically useful β- and γ-chlorinated ketones (40 examples). Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on gram scale. </p> </div> </div> </div>

Manganese-Catalyzed Electrochemical Deconstructive Chlorination of Cycloalkanols via Alkoxy Radicals

“…Ongoing studies are focused on further applications of earth-abundant transition metals in synthetic organic electrochemistry, and these results will be reported in due course. 27 ■ ASSOCIATED CONTENT * S Supporting Information…”

“…Furthermore, the combination of recirculating flow electrochemistry and continuous inline purification was employed to access products on gram scale. Ongoing studies are focused on further applications of earth-abundant transition metals in synthetic organic electrochemistry, and these results will be reported in due course …”

Selective Carbon–Carbon Bond Cleavage of Cyclopropanols

“…In 2019, Browne and Morrill published an electrochemical β-chlorination of cyclopropyl alcohols using catalytic amounts of Mn(OTf) 2 (Scheme 117). 260 They propose that Mn(II) is electrochemically oxidized to Mn(III), which, upon reacting with cyclopropyl alcohol 554, generates an alkoxy radical that ring opens to form a β-keto radical. This radical is then trapped with the Mn(III)X 2 Cl formed in situ, resulting in Mn turnover as well as formation of the desired product 555.…”

Electrophotochemical Ce-Catalyzed Ring-Opening Functionalization of Cycloalkanols under Redox-Neutral Conditions: Scope and Mechanism

“…45 In this work, by applying earth-abundant simple Ce chloride as a catalyst, 46,47 we report an EPC LMCT process to enable βscission of cycloalkanols with different ring sizes and formation of C−CN, C−C, C−S, C−oxime, etc., bonds without the formation of C-halides, which was inevitable in previous electrochemical synthetic methods (Scheme 2c). 45,48 ■ RESULTS AND DISCUSSION Reaction Optimization. Our study starts from examining the ring-opening reaction of 1-methylcyclohexanol (1) via EPC catalysis with constant current and blue light irradiation in an undivided cell (Table 1).…”