Regioselective Synthesis of Carbonyl-Containing Alkyl Chlorides via Silver-Catalyzed Ring-Opening Chlorination of Cycloalkanols

Abstract

A novel and regioselective approach to carbonyl-containing alkyl chlorides via silver-catalyzed ring-opening chlorination of cycloalkanols is reported. Concurrent C(sp(3))-C(sp(3)) bond cleavage and C(sp(3))-Cl bond formation efficiently occur with good yields under mild conditions, and the chlorinated products are readily transformed into other useful synthetic intermediates and drugs. The reaction features complete regioselectivity, high efficiency, and excellent practicality.

Sequential Silver‐Catalyzed Oxidative Cyclization Reactions of Unprotected 2‐Alkynylanilines to Anthranils

“…Direct evidence for C–O bond formation through a reductive elimination step at a monometallic silver center has been described recently . Moreover, Ag III intermediates were proposed in the synthesis of 2‐aryl‐2 H ‐benzotriazoles from azobenzenes …”

Radical-Mediated Hetaryl Functionalization of Nonactivated Alkenes through Distal ipso-Migration of O- or S-Hetaryls

“…Moreover, 2a was a suitable substrate for a click reaction, reacting with ethynylbenzene to give the corresponding triazole 6 in 97% yield. 19 Benzotriazole 7 was obtained by the reaction of 2a with benzyne, generated in situ. 20 Scheme 4 Silylhetarylation of nonactivated alkenes.…”

Radical‐Promoted C−C Bond Cleavage: A Deconstructive Approach for Selective Functionalization

“…Kurzaufsätze quently,the M n ÀX species are oxidized under strong oxidative conditions into the high-oxidative M n+2 À X species.U pon single-electron transfer (SET) an alkoxy radical (H)i s achieved at the same time as the release of M n+1 À X.W elldesigned strategies combining metal catalysts, XÀYreagents, and oxidants have enabled the groups of Narasaka, [20] Murakami, [21] Zhu, [22] Loh, [23] Duan, [24] Zhang, [25] Lopp, [26] and Orellana, [27] to achieve aw ide range of deconstructive functionalizations of cycloalkanols.A na lternative protocol was reported by Chiba, [28] where an alkoxy radical (J)w as added to av inyl azide.…”