Radical-mediated reduction of the dithiocarbamate group under tin-free conditions

Abstract

Reductive desulfurisation of dithiocarbamates is conveniently achieved using H(3)PO(2)-Et(3)N-ACCN in refluxing dioxane. Fused and spirocyclic β-lactams, prepared through 4-exo trig carbamoyl radical cyclisation-dithiocarbamate group transfer reactions, are reduced without fragmentation of the strained 4-membered ring. Diethyl tetraacetyl-d-glucopyranosyl dithiocarbamate is selectively reduced with or without acyloxy group migration depending on reaction conditions and choice of reductant. Deuterium incorporation from D(3)PO(2)-Et(3)N is observed for a system involving a nucleophilic radical intermediate, but not in the case of the electrophilic radical obtained through acyloxy group migration on a glucose derivative.

A General Approach to Site‐Specific, Intramolecular C−H Functionalization Using Dithiocarbamates

“…We found the versatility of the dithiocarbamate group to be similar to that of the xanthate group,with awide variety of CÀHt ransformations easily achieved via subsequent radical or polar processes (Figure 4). [21] Fore xample,r adical mediated allylation, deuteration, [21b] and azide transfer provide valuable CÀHd iversification products in good yields.C hugaev-type elimination of the alkyl dithiocarbamate provides formal dehydrogenation product 24 in nearly quantitative yield. [21c] Facile cleavage of the dithiocarbamate also enables site-specific C À Ht hiolation in good yield.…”

A convenient method for palladium‐catalyzed reductive deuteration of organic substrates using deuterated hypophosphite in D2O

“…There have been limited examples of the use of deuterated hypophosphorous acid and its salts for this application. Oshima and coworkers reported the D 3 PO 2 ‐mediated deuteration of organic halides via a radical chain process, which was applied to the radical deuteration of a dithiocarbonate group by Grainger and coworkers . Reductive deuteration using deuterium iodide catalytically generated from D 3 PO 2 and a small amount of I 2 in AcOD was also reported by Fry and coworkers…”

Synthesis of 5‐amino‐1,3,4‐thiadiazoles containing dithiocarbamate groups

“…The dithiocarbamate group is an important functional group in synthetic organic chemistry and medicinal chemistry . It is a valuable pharmacophore that induces various biological activities when incorporated in a structure.…”

“…[11][12][13][14] The dithiocarbamate group is an important functional group in synthetic organic chemistry and medicinal chemistry. [15][16][17][18][19][20][21][22][23][24][25] It is a valuable pharmacophore that induces various biological activities when incorporated in a structure. Recently, various heterocyclic compounds containing dithiocarbamate groups including chromone-dithiocarbamate, [26] triazole-dithiocarbamates, [27] benzodioxole-dithiocarbamates, [28] benzimidazole-dithiocarbamates, [29] indoledithiocarbamates, [30] and quinazolinone-dithiocarbamate [31] have been introduced as efficient building blocks with anticancer and antibacterial activities (Scheme 1B).…”