α-Thiocarbonyl synthesisviathe Fe^II-catalyzed insertion reaction of α-diazocarbonyls into S–H bonds

Abstract

Fe(OTf)2 was used to catalyze the insertion reaction of α-diazocarbonyls into S–H bonds at 40 °C.

Recent Advances in Iron‐Catalyzed Chemical and Enzymatic Carbene‐Transfer Reactions

“…described the iron‐catalyzed S−H carbene‐insertion reactions using α‐diazocarbonyls (21) as carbene precursor (Scheme 31). [49] During this study, commercially available iron catalysts such as Fe(OTf) 2 , FeCl 2 and FeCl 3 were screened for the reaction of thiophenol and methyl α‐phenyl‐α‐diazoacetate and found Fe(OTf) 2 as the best iron salt for catalyzing this reaction. Besides, FeCl 2 and FeCl 3 were also able to catalyze the reaction under the same reaction conditions, but less conversion was recorded with these catalysts.…”

The Power of Iron Catalysis in Diazo Chemistry

“…In 2019, the Ollevier group were able to showcase a simple iron salt [Fe(OTf) 2 ] as an efficient catalyst for the insertion reaction of -diazo esters and unprecedented -diazo ketones with both alkaneand arenethiols (Scheme 14). 46 The reaction used Fe(OTf) 2 at 10-20 mol% loading at 40 °C in DCM to give the S-H insertion products in up to 96% yield. Control experiments and a H/D KIE study pointed towards a stepwise mechanism that involves the attack of the thiol on the iron carbene intermediate leading to an ylide intermediate that dissociates to give the targeted insertion product.…”

Assembly of Thiosubstituted Benzoxazoles via Copper-Catalyzed Coupling of Thiols with 5-Iodotriazoles Serving as Diazo Surrogates

“…While N–H and O–H insertions have been known for a long time and are well developed, the insertion into the S–H bond has been much less investigated. Nevertheless, several methods involving Cu, Rh, and Fe catalysts have been reported.…”